Polyurethane based pigment dispersants which contain reactive double bonds

ABSTRACT

Polymeric urethane dispersants with solubilizing polymer chains and with reactive carbon to carbon double bonds are described. The reactive double bonds facilitate molecular weight build-up of the dispersant on dispersed particles (enhancing colloidal stability) or enhance the ability of the dispersants to be crosslinked into a matrix material.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part from U.S. application Ser.No. 11/916,661 filed on Dec. 6, 2007, now U.S. Pat. No. 8,338,558, whichclaims priority from PCT Application Serial No. PCT/US2006/021250 filedon Jun. 1, 2006, which claims the benefit of U.S. ProvisionalApplication Ser. No. 60/688,011 filed on Jun. 7, 2005 and further claimspriority from copending U.S. Provisional Application Ser. No. 61/139,847filed on Dec. 22, 2008.

FIELD OF INVENTION

The invention relates to the polyurethane dispersants with carbon tocarbon double bonds themselves and to their use for dispersing particles(e.g., pigments) in liquid media. In the first embodiment, once thedispersion of particles has been made, the dispersants may becrosslinked with a suitable crosslinking agent (e.g., polyamine or viafree radicals) to lock them onto the particle surface. Alternatively,the dispersions may be utilized in paints, coatings, inks or otherformulations where the binder material contains reactive unsaturationwhich is cured after the addition of the dispersion. The polyurethanesmay have linear or non-linear backbones.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 3,393,162 to ICI titled Block and Graft CopolymerDispersants claims a process for coating solid particles with organicpolymeric material including the steps of dispersing said particles in aliquid containing block and/or graft copolymers, said copolymerscomprising polymeric components of different degrees of polarity,varying the polarity of the liquid to precipitate at least one but notall of said polymeric components on said particles, whereas said blockand/or graft copolymers thereafter function as a dispersion stabilizerfor the particles.

U.S. Pat. No. 6,262,152 to E. I. du Pont discloses dispersionscontaining a liquid vehicle (which can be aqueous, semi-aqueous),organic or inorganic particles (or mixtures) that are insoluble in theliquid vehicle and a polymeric dispersant, having improved stabilitywhen the insoluble segment(s) contains cross-linking groups which arecross-linked to itself or a cross-linking compound to form anencapsulated network that entraps the particles, which are particularlyuseful for paints or inks in coating and printing applications.

SUMMARY OF THE INVENTION

Polyurethane dispersants with on average at least one reactive carbon tocarbon double bond per molecule can be made. They are useful in makingdispersants that either a) form more stable dispersions due to chainextension/crosslinking reactions (by Michael addition reaction with apolyamine or by free radical mechanisms) of the dispersants after saiddispersants have adsorbed themselves on a particle surface or b) can befree radically crosslinked into various binders or continuous phases ifsuch binders/continuous phases are reactive with carbon to carbon doublebonds.

DETAILED DESCRIPTION OF THE INVENTION

Dispersants containing reactive carbon to carbon double bonds serve tosolve problems in 2 areas. Dispersants with reactive carbon to carbondouble bonds can co-cure with unsaturated binder systems e.g., sheet orbulk molding compounds or radiation cure systems (UV, electron beam orthermal). Use of a conventional dispersant in coatings, inks or resinsystems (e.g., sheet molding compounds) which cure throughpolymerization after application can lead to a reduction in performanceof the coating or article. As normally the dispersant is a non-reactivecomponent in the curing system, it may (i) serve to extend cure time,(ii) lead to softening or plasticisation of the final film (iii)potentially be exuded from the final film which may manifest itself asblooming. The presence of reactive double bonds within the dispersant ofthis disclosure enables the dispersant to be incorporated and bondedinto the cured matrix during polymerization thereby reducing oreliminating the negative effects of the conventional dispersant.

The stability of pigment dispersions with conventional dispersants canbe adversely affected by changes in conditions e.g., when the pigmentdispersion is letdown into the coating composition or if it experienceselevated temperatures or a change to a different solvent mixture.Introduction of other pigments or particulate matter may also causepreferential adsorption of the dispersant by a second pigment sourceleading to destabilization of the original pigment dispersion due todispersant depletion from the initial pigment.

Conventional dispersants adsorb onto pigment surface and equilibrium isestablished with free dispersant in continuous phase. For a pigmentdispersant to remain effective in providing a steric and/orelectrostatic barrier to flocculation the conventional dispersant mustremain substantially adsorbed to the pigment. The equilibrium positioncan be affected by change in temperature, change in solvent, etc. Thestrength of the adsorption (i.e., equilibrium position between free andadsorbed dispersant) will also vary depending on the nature of thepigment.

Although not wishing to be bound to any specific mode of action, thefollowing schematic illustration is included to help explain theproblem.

If the dispersant can be crosslinked or chain extended to a highermolecular weight after adsorption to the pigment surface, it will thenbe locked in place or become less soluble in the continuous phase andtherefore much less able to desorb. Therefore, the stability of thepigment dispersion is much less prone to be adversely affected by thechanges in environment (vehicle composition, temperature, etc.) asdiscussed above.

Polyurethane based dispersants enable ready incorporation of reactivedouble bonds in a simple single stage, single pot reaction. The reactivedouble bonds can either co-cure with a reactive binder system or reactwith external crosslinkers such as polyamines to form an encapsulatednetwork thereby offering flexibility in dispersant design andapplication area.

Embodiment 1

One embodiment of this invention involves modification of dispersantshaving laterally attached solubilizing side chains and essentiallylinear polyurethane backbones to contain one or more carbon to carbondouble bonds. These are shown in the following schematic representationswhere circles represent repeating units from monomer and the wigglylines represent either lateral solubilizing side polymer chains orterminal solubilizing chains. X′ represents optional acid or aminogroups (“c”) described later. The first figure represents a polyurethanedispersant without any carbon to carbon double bonds.

The reactive double bond can be incorporated in several ways either ata) end of solubilizing chain or b) from monomeric species orcombinations. Three possibilities from a plethora of possible structuresare shown below.

Embodiments 1, 2, and 3 are similar in that all have a polyurethanebackbone and solvent solubilizing chains. Embodiment 1 differs fromembodiments 2 and 3 in that most of the urethane forming monomers aremonofunctional or difunctional (rather than tri or higherfunctionalities) such that the polymer backbone (defined as themolecules directly between the reactive groups of each difunctionalmonomer) is a linear backbone. The laterally attached side chains(solubilizing chains) in this embodiment are chemically bound as a sidechain to the initial monomer and thus are lateral side chains to thepolyurethane backbone when it is formed. The polyurethane dispersants ofembodiment 1 may be prepared by any polyurethane synthesis method knownto the art and are readily obtainable or obtained by reacting together:

a) one or more polyisocyanates having an average functionality of from2.0 to 2.5;

b) one or more compounds (solvent-solubilizing) having at least onepolyester, polyether, polyacrylate or polyolefin chain and at least twogroups which react with isocyanates which are located at one end of thecompound such that the polyester, polyether or polyacrylate chain(s) islaterally disposed in relation to the polyurethane polymer backbone; Aportion of these chains, up to 100%, may contain one or more carbon tocarbon double bonds.

c) optionally, one or more compounds having an acid or amino group,including salts thereof, and at least two groups which react withisocyanates;

d) optionally, one or more formative compounds having a number averagemolecular weight of from 32 to 3,000 which have at least two groupswhich react with isocyanates; A portion of these compounds, up to 100%,may contain one or more carbon to carbon double bonds.

e) optionally, one or more compounds which act as polyurethane chainterminators which contain one group which reacts with isocyanates; Aportion of these compounds, up to 100%, may contain one or more carbonto carbon double bonds.

f) optionally, one or more compounds which act as chain terminatorswhich contain a single isocyanate group. A portion of these compounds,up to 100%, may contain one or more carbon to carbon double bonds.

g) As noted hereinbefore, the polyurethane dispersants of embodiment 1have an essentially linear backbone and consequently it is muchpreferred that components (b), (c) and (d) contain only two groups whichreact with isocyanates. It is also preferred that component (a) has afunctionality of from 2.1 to 2.0 and especially about 2 since this alsolimits any cross-linking/branching between chains of the polyurethanedispersants.

Double bonds can be present in any or all of the components (b), (d),(e) or (f). It is essential for the invention that double bonds arepresent in at least one of these components.

It is preferred that the average functionality of carbon to carbondouble bonds in the dispersant molecule is at least one. It isespecially preferred that the average functionality of double bonds inthe dispersant molecule is at least about two.

It is preferred in some embodiments that component (f) is absent.

It is preferred that double bond(s) are present in (b) and/or (d) and/or(e). It is especially preferred that the double bonds are present incomponent (e).

It is preferred that the double bond or bonds in component (b), ifpresent, are located at the opposite end of the chain to the isocyanatereactive groups.

It is preferred that the double bonds present in the dispersant arereactive in polymerization with other unsaturated components used inreactive coatings such as radiation curable coatings and inks or sheetmolding compounds. The double bonds present in the dispersant shouldtherefore copolymerize with monofunctional and polyfunctional(meth)acrylate monomers and oligomers and styrenic monomers.

It is preferred that the double bonds present in the dispersant areactivated towards the addition of primary and secondary amines.

It is preferred that the double bonds present in the dispersant arepresent in methacrylate or acrylate ester functionalities. It isespecially preferred that they are present in acrylate esters.

Examples of materials for component (e) that contain one or more doublebonds are of two types.

1) Monomeric.

-   -   It is preferred that the isocyanate reactive group is hydroxy.        Examples include hydroxyethyl acrylate, hydroxypropyl acrylate,        pentaerythritol triacrylate, hydroxyethyl methacrylate,        hydroxypropyl methacrylate, allyl alcohol.

2) Polymeric.

Polymeric types include

i) Polyalkylene glycol acrylates (and methacrylates). Example of generalstructure shown for PEG/PPG (alk)acrylate.

where R=H or alkyl. R is preferably H or methyl. R is especiallypreferred to be H.

Several grades are commercially available e.g., from Cognis.

n+m=2 to 100, preferred 3 to 50, especially 5 to 50

ii) Monohydroxy polyester (meth)acrylates.

A specific example for illustrative purposes of a monohydroxy polyester(meth)acrylate is obtained from polymerization of ε-caprolactone in thepresence of hydroxyethyl acrylate.

Examples of materials for component (d) that contain one or more doublebonds are glycerol acrylate and glycerol methacrylate.

One method used for generating materials of component b which contain adouble bond is to react a monohydroxy polymer chain containing a carbonto carbon double bond onto a diisocyanate with differential reactivityof the two isocyanates groups (such as 2,4-TDI) and then react thatadduct with a dialkanolamine such as diethanolamine to generate thedihydroxy adduct. The reactivity of the carbon to carbon double bondtowards Michael addition of the amine is desirably such as to competesignificantly with the addition of the amine to the isocyanate residue.An illustrative example shows the reaction for a (meth)acrylate endedmonohydroxy polylactone chain. The desired product together with thepotential undesired product are illustrated. The desired reaction willbe more favoured for methacrylate functional chains (with R=Me) in thefollowing scheme.

Another way a (meth)acrylate functionality could be introduced is to usea modification of the method described in EP43966.

In EP43966 compounds of the general formulae

are disclosed.

From a translation of the original German patent R³ is described asfollows

R³ is a protective group optionally removable again by cleavage. This isintroduced before the acetal or ketal cleavage, by reacting the hydroxylgroup with a compound which is monofunctional and has a group reactivetowards the hydroxyl group. Here, the reaction can take place bysubstitution or addition. An example of a substitution reaction is thereaction of the hydroxyl group with an alkyl halide, e.g., methylchloride, or an alkyl aryl halide, e.g., benzyl chloride, wherein thehydrocarbon residue can have 1 to 12 carbon atoms. An example of asuitable addition reaction is the reaction of the hydroxyl group of thepolyether with an organic mono-isocyanate, e.g., an alkyl or arylmono-isocyanate, or a vinyl compound, e.g., acrylonitrile, methylacrylate or methyl vinyl ketone.

The blocking of the free hydroxyl group on the opposite polyether chainend to the starting alcohol can however be effected under conditionssuch that, if desired, the protective group can be cleaved off again.Thus, for example, it is possible to esterify the hydroxyl group with anorganic monocarboxylic acid or an acid chloride. Correspondingesterifications are also possible with other acids, e.g., sulphonicacid. After the cleavage of the ketal or acetal group and after thepolymerization of the 1,2 or 1,3-diol formed, the end-blocking estergroup can be removed by saponification.

A preparation is therefore illustrated by the following scheme

If the blocking of the hydroxy group were carried out with(meth)acryloyl chloride or an isocyanoto(meth)acrylate, then a(meth)acrylate ended material would be realized.

Methacryloyl chloride may also be used in place of acryloyl chloride togenerate a methacrylate functionality.

The preparation of the polyurethane polymer/prepolymer may be carriedout in the presence of a catalyst. Particularly preferred catalysts aretin complexes of aliphatic acids such as dibutyl tin dilaurate (DBTDL)and tertiary amines.

The preparation of the polyurethane polymer/prepolymer is carriedoptionally in the presence of a polymerization inhibitor such ashydroquinone or butylated hydroxy toluene.

The preparation of the polyurethane polymer/prepolymer may be carriedout in an inert atmosphere, which may be provided by any of the inertgases of the Periodic Table, but is preferably nitrogen. The preparationof the polyurethane polymer/prepolymer may also be carried out under anatmosphere of air to assist inhibition of the polymerization of reactivecarbon to carbon double bonds present. When the presence of oxygen isdesired to assist inhibition of the polymerization of reactive carbon tocarbon double bonds present, but flammability of the polymerizingmixture is a concern the preparation may be carried out under anatmosphere of depleted oxygen which typically contains 1-10% oxygen.

The essential feature of the polyurethane polymer according toembodiment 1 is that it comprises a predominantly linear polyurethanepolymer backbone containing defined amounts of lateral polymeric sidechains (solvent solubilizing) which may be poly(alkylene oxide),polyester, poly(alk)acrylate or polyolefin. There will thus be manyvariants which will be obvious to the skilled addressee regarding theratio of isocyanate groups to isocyanate reactive groups including theformulation of prepolymers which have residual isocyanate functionality.In one case, the ratio of total isocyanate groups provided by component(a) is less than the total number of isocyanate reactive groups providedby component (b) and components (c) (d) and (e) when present. Anyterminal isocyanate reactive groups may be reacted.

Whereas, the polyester, polyether, polyacrylate or polyolefin chains maycontain a terminating hydroxy group remote from the polyurethanebackbone it is much preferred that such chains carry a [terminating]group which is not reactive with isocyanates since this restricts anycross-linking during the preparation of the dispersant. The terminatinggroup remote from the polyurethane backbone may contain a carbon tocarbon double bond otherwise it is preferred that it is aC₁₋₅₀-hydrocarbyl group. The hydrocarbyl group may be optionallybranched alkyl, cycloalkyl, aryl or aralkyl. In some aspects, it isdesirable that the hydrocarbyl group contain one or more carbon tocarbon double bonds. The cycloalkyl group is preferably C₃₋₆-cycloalkylsuch as cyclopropyl and especially cyclohexyl. The aryl group ispreferably C₆₋₁₀-aryl such as naphthyl and especially phenyl which maybe substituted by halogen, C₁₋₂₀-alkyl or C₁₋₂₀-alkoxy. The aralkylgroup is preferably 2-phenylethyl and especially benzyl where the phenylring is optionally substituted by halogen, C₁₋₂₀-alkyl or C₁₋₂₀-alkoxy.The hydrocarbyl group here and elsewhere in this disclosure is desirablysubstantially hydrocarbon but in some aspects up to 1, 2, or 3 oxygen,nitrogen, or sulfur atoms may be present for every 10 carbon atoms.

The length of the alkyl terminating group of the polyester, polyether,polyacrylate, or polyolefin chain depends to a large extent on thenature of the organic medium. Thus, for example, when the vehicle is apolar organic liquid, the hydrocarbyl group is preferably C₁₋₁₂-alkylwhich may be linear or branched. The hydrocarbyl group includes ethyl,propyl, isopropyl or mixtures thereof. When the polyurethane dispersantcontains polyether side chains it is preferred that the terminatingalkyl group is C₁₋₄ alkyl, for instance methyl, because of their readycommercial availability. When the vehicle is a non-polar organic liquidit is preferred that the terminating alkyl group contains greater than 8carbon atoms. It is also preferred that the alkyl group is branchedsince this aids solubility in the non-polar organic liquid.

The alkylene moiety of the (C₂₋₄-alkylene oxide) group may be linear orpreferably branched and may be obtained by (co)polymerization ofalkylene oxides such as ethylene oxide, propylene oxide and butyleneoxide or from tetrahydrofuran. Copolymers may be random or blockcopolymers.

The polyester chain is preferably obtainable or obtained from a hydroxycarboxylic acid containing from 1 to 26 carbon atoms or a lactonethereof. The choice of hydroxy carboxylic acid is largely influenced bythe nature of the organic medium itself. Where the vehicle is a polarorganic liquid, the hydroxy carboxylic acid preferably contains up to 8carbon atoms and where the vehicle is a non-polar organic liquid thehydroxy carboxylic acid preferably contains more than 8 carbon atoms. Itis particularly preferred that the polyester chain is obtainable fromtwo or more different hydroxy carboxylic acids or lactones thereof sincethis aids solubility in the organic medium. The hydroxy carboxylic acidmay be saturated or unsaturated, linear or branched.

Examples of suitable hydroxy carboxylic acids are glycolic acid, lacticacid, 5-hydroxy valeric acid, 6-hydroxy caproic acid, ricinoleic acid,12-hydroxy stearic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoicacid, 5-hydroxydecanoic acid and 4-hydroxydecanoic acid. Examples ofsuitable lactones are β-propiolactone and optionally C1-6-alkylsubstituted δ-valerolactone and ε-caprolactone such asβ-methyl-δ-valerolactone; δ-valerolactone; ε-caprolactone; 2-methyl,3-methyl, 4-methyl, 5-tert butyl, 7-methyl-, 4,4,6-trimethyl-, and4,6,6-trimethyl-ε-caprolactone; including mixtures thereof. Polyesterchains derivable from δ-valerolactone and ε-caprolactone are especiallypreferred.

The polyacrylate chains are preferably obtainable or obtained by(co)polymerizing C₁₋₆-(alk)acrylate esters (where “(alk)” meansoptionally substituted with a C_(1-C6) alkyl on the double bond) andespecially (meth)acrylate esters (e.g. polymers from acrylic acid(optionally C₁₋₆ alkyl substituted) or esters from C₁₋₁₈ (morepreferably C₁₋₈) alcohols and acrylic or C₁₋₆ alkyl substituted acrylicacid).

As disclosed hereinbefore, the polyurethane dispersants may containmixtures of polyester, polyether, polyacrylate, and polyolefinsolvent-solubilizing chains.

By way of an obvious variant, the polyester, polyether, polyacrylate,and polyolefin solvent solubilizing chains may themselves be mixtures ofsuch chains. Thus, for example, the polyester and polyacrylate sidechains may contain a polyether moiety and so on.

The number-average molecular weight of the solvent-solubilizingpolyester, polyether, polyacrylate, or polyolefin chains in thepolyurethane dispersant is preferably not greater than 10,000, morepreferably not greater than 4,000 and especially not greater than 2,500.It is also preferred that the number-average molecular weight of thelateral polyester, polyether and polyacrylate chains is not less than300, more preferably not less than 600 and especially not less than 800.

The lateral side chain polyester, polyether, polyacrylate or polyolefinchains in embodiment 1 are connected to polyurethane backbone by oxygenand/or nitrogen atoms which are the residue of terminating hydroxy andamino (primary and secondary) groups of the polyester, polyether,polyacrylic (especially polyacrylate) or polyolefin.

When the lateral side chain is a polyether of embodiment 1, it ispreferably the residue of a polyether which contains either two hydroxylgroups or one hydroxyl and one secondary amino group (both predominantlyat one end of the lateral side chain) which react with isocyanates. Thehydroxyl and/or amino groups are preferably separated from each other byup to 6 carbon atoms. In one embodiment, when the polyether contains twohydroxyl groups which react with isocyanates, they are preferablyseparated by up to 17 atoms, especially 16 carbon atoms and one nitrogenatom. It is also preferred that the two hydroxyl groups are separated bynot less than 5 atoms, especially 4 carbon atoms and one nitrogen atom.It is also possible to prepare the dispersant from a polyether whichcontains two amino groups (i.e., primary and/or secondary amino groups)which react with isocyanates but this is less preferred.

When the lateral side chain of embodiment 1 is a polyester, it ispreferably the residue of the polyester which contains two hydroxylgroups at one end of the polyester chain which react with isocyanates.The hydroxyl groups are also preferably separated by up to 17 atoms,especially 16 carbon atoms and one nitrogen atom. It is especiallypreferred that the two hydroxyl groups are separated by not less than 5atoms.

When the lateral side chain is a polyacrylate of embodiment 1, it ispreferably the residue of a polyacrylate which contains two hydroxygroups at one end of the polyacrylate chain which react withisocyanates. The two hydroxyl groups are preferably separated by up to 4carbon atoms, for example, 2 carbon atoms. In one embodiment, thepolyacrylate is present and in another embodiment the polyacrylate isabsent.

When the lateral side chain of embodiment 1 is a polyolefin, it ispreferably the residue of a polyolefin which contains either twohydroxyl groups or one hydroxyl and one secondary amino group whichreact with isocyanates at one end of the polyolefin chain. The hydroxyland amino groups are preferably separated by up to 6 carbon atoms. Whenthe polyolefin contains two hydroxyl groups which react withisocyanates, they are preferably separated by up to 17 atoms, especially16 carbon atoms and one nitrogen atom. It is also preferred that the twohydroxyl groups are separated by not less than 5 atoms, especially 4carbon atoms and one nitrogen atom. It is also possible to prepare thedispersant from a polyolefin which contains two amino groups (i.e.,primary and/or secondary amino groups) which react with isocyanates butthis is less preferred.

The dispersant may also optionally contain an acid and/or amino group,including salts thereof, since such groups have been found to improvethe dispersibility of some particulate solids. The amount of acid and/oramino groups in the polyurethane dispersant is preferably from 10 to180, more preferably from 20 to 110, and especially from 20 to 60milliequivalents for each 100 g polyurethane dispersant. It is preferredthat the dispersant contains acid and/or amino groups. For acid, it ispreferred that these are carboxylic acid. For amino groups, it ispreferred that these are tertiary or aromatic.

When the acid group is in the form of a salt, it may be the salt of analkali metal such as sodium, potassium or lithium, a salt of an aminesuch as C₁₋₈-alkylamine or C₁₋₈-alkanolamine or a salt of a quaternaryammonium cation such as a C₁₋₈-alkyl quaternary ammonium cation orbenzalkonium cation. The amino group may be quaternised. This may beachieved, for example, by reaction with a dialkyl sulphate, such asdimethyl sulphate or benzyl chloride. Preferably, the acid group, whenpresent, is in the form of the free acid.

When the amino group is in the form of a salt, it may be the salt of aninorganic or organic acid. Examples of such acids are inorganic acidssuch as hydrochloric acid and organic acids such as those containingcarboxylic acid group(s) (e.g., acetic acid), sulphonic acid group(s) orphosphonic acid groups. Preferably, the amino group, when present, is ina non-ionized form.

The polyurethane dispersant may in addition to lateral side chains alsohave terminal solvent solubilizing polyester, polyether, polyacrylate orpolyolefin chains. Such chains are similar to those describedhereinbefore for the lateral chains but are obtainable from compoundshaving only the one group which reacts with isocyanates. Thesolvent-solubilizing chains with one reactive group are used extensivelyin embodiments 2 and 3.

The total weight percentage of the solvent-soluble lateral and terminalchains in the polyurethane dispersant is preferably not less than 20%,more preferably not less than 30% and especially not less than 40%. Thesolvent soluble lateral and terminal chains are similar in that bothtypes are primarily chemically bonded to the polymer backbone at one endof the chains and thus the non-bonded end of the chain has significantmobility to extend into the solvent phase. It is also preferred that thetotal weight percentage of solvent-soluble lateral and terminal chainsin the polyurethane dispersant is not greater than 90%, more preferablynot greater than 80%, for instance 45% to 80% or 60% to 78%. In oneembodiment, the total weight percentage of solvent-soluble lateral andterminal chains in the polyurethane dispersant is not greater than 70%,for instance 55% to 65%.

The weight percentage of solvent-soluble lateral chains in thepolyurethane dispersant is preferably not less than 5%, more preferablynot less than 15% and especially not less than 25% or not less than 35%.

General Uses of Dispersant

According to the invention, there is provided a non-aqueous compositioncomprising a particulate solid, an organic medium and a polyurethanedispersant having an essentially linear backbone with laterally attachedsolvent-solubilizing side chains of a polyester, a polyacrylic, apolyether or a polyolefin including mixtures of such side chains. Thepolyurethane dispersant is further characterized in that it alsocomprises on average at least one group containing carbon to carbondouble bonds (unsaturation). The groups containing the carbon to carbondouble bonds may be incorporated such that they are part of the vehiclesoluble chains or vehicle insoluble portion(s) of the dispersant. Thevehicle soluble or the vehicle insoluble portion of the dispersant canbe close to the backbone or pendant from the backbone, depending on thevehicle and particle system chosen. In this disclosure, vehicle willrefer to the continuous phase in which the particulate is dispersed. Itmay be water, organic solvents or blends thereof. In some preferredembodiments, the vehicle soluble portions of the dispersant extend fromthe dispersant backbone into the vehicle phase.

The invention also includes the dispersant materials themselves as wellas the composition in which they are used such as a paint, coating, inkor molding compound. According to the invention, there is provided anon-aqueous composition comprising a particulate solid, an organicmedium and a polyurethane dispersant (in embodiment 1 having anessentially linear backbone with laterally attached solvent solubilizingside chains) of polyester, polyacrylic (especially a polyacrylate),polyether or polyolefin including mixtures of such side chains(embodiment 1) or essentially non-linear backbone withsolvent-solubilizing side chains at the termini and optionally laterallyattached (embodiments 2 and 3). The optimum choice of the solventsolubilizing side chain will be dependent on the polarity of the vehicle(e.g., organic medium). In one embodiment, the polyolefin is present andin another embodiment the polyolefin is absent.

In one embodiment where non-aqueous vehicle is desirable, the vehicleoptionally contains 5 wt. % or less water, preferably less than 2 wt. %,more preferably less than 0.5 wt. % and most preferably no water.

The particulate solid present in the composition may be any inorganic ororganic solid material which is substantially insoluble in the organicmedium at the temperature concerned and which it is desired to stabilisein a finely divided form therein.

Examples of suitable solids are pigments for solvent inks; pigments,nano-materials such as metal oxides, metals, nanotubes, etc., extendersand fillers for paints and plastics materials; dyes, especially dispersedyes; optical brightening agents and textile auxiliaries for solventdyebaths, inks and other solvent application systems; solids foroil-based and invert-emulsion drilling muds; dirt and solid particles indry cleaning fluids; particulate ceramic materials; magnetic materialsand magnetic recording media, fire retardants such as those used inplastics materials and biocides, agrochemicals and pharmaceuticals whichare applied as dispersions in organic media.

A preferred particulate solid is a pigment from any of the recognisedclasses of pigments described, for example, in the Third Edition of theColor Index (1971) and subsequent revisions of, and supplements thereto,under the chapter headed “Pigments”. Examples of inorganic pigments aretitanium dioxide, zinc oxide, Prussian blue, cadmium sulphide, ironoxides, vermilion, ultramarine and the chrome pigments, includingchromates, molybdates and mixed chromates and sulphates of lead, zinc,barium, calcium and mixtures and modifications thereof which arecommercially available as greenish-yellow to red pigments under thenames primrose, lemon, middle, orange, scarlet and red chromes. Examplesof organic pigments are those from the azo, disazo, condensed azo,thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone,isodibenzanthrone, triphendioxazine, quinacridone, perylene,diketopyrrolopyrrol (DPP), and phthalocyanine series, especially copperphthalocyanine and its nuclear halogenated derivatives, and also lakesof acid, basic and mordant dyes. Carbon black, although strictlyinorganic, behaves more like an organic pigment in its dispersingproperties. Preferred organic pigments are phthalocyanines, especiallycopper phthalocyanines, monoazos, disazos, indanthrones, anthranthrones,quinacridones, perylene, diketopyrrolopyrrol (DPP), and carbon blacks.

Other preferred particulate solids are: extenders and fillers such astalc, kaolin, silica, barytes and chalk; particulate ceramic materialssuch as alumina, silica, zirconia, titania, silicon nitride, boronnitride, silicon carbide, boron carbide, mixed silicon-aluminiumnitrides and metal titanates; particulate magnetic materials such as themagnetic oxides of transition metals, especially iron and chromium,e.g., gamma-Fe₂O₃, Fe₃O₄, and cobalt-doped iron oxides, calcium oxide,ferrites, especially barium ferrites; and metal particles, especiallymetallic iron, nickel, cobalt and alloys thereof; agrochemicals such asthe fungicides flutriafen, carbendazim, chlorothalonil and mancozeb andfire retardants such as aluminium trihydrate and magnesium hydroxide.Nanomaterials includes metal oxides such as oxides of alumina,zirconium, zinc, ferrous silica and titanium etc., and metals such assilver, gold, copper etc. and nanotubes such as single and multi layercarbon nanotubes, and others such as nanoclays, dendrimiers, quantumdots, LED or OLED etc.

In embodiments where the vehicle is an organic medium present in thecomposition, it is preferably a polar organic medium or a substantiallynon-polar aliphatic or aromatic hydrocarbon or halogenated hydrocarbon.By the term “polar” in relation to the organic medium is meant anorganic liquid or resin capable of forming moderate to strong bonds asdescribed in the article entitled “A Three Dimensional Approach toSolubility” by Crowley et al. in Journal of Paint Technology, Vol. 38,1966, at page 269. Such organic media generally have a hydrogen bondingnumber of 5 or more as defined in the above mentioned article.

Examples of suitable polar organic liquids are amines, ethers,especially lower alkyl ethers, organic acids, esters, ketones, glycols,alcohols and amides. Numerous specific examples of such moderatelystrongly hydrogen bonding liquids are given in the book entitled“Compatibility and Solubility” by Ibert Mellan (published in 1968 byNoyes Development Corporation) in Table 2.14 on pages 39-40, and theseliquids all fall within the scope of the term polar organic liquid asused herein.

Preferred polar organic liquids are dialkyl ketones, alkyl esters ofalkane carboxylic acids and alkanols, especially such liquids containingup to, and including, a total of 6 carbon atoms. As examples of thepreferred and especially preferred liquids, there may be mentioneddialkyl and cycloalkyl ketones, such as acetone, methyl ethyl ketone,diethyl ketone, di-isopropyl ketone, methyl isobutyl ketone, di-isobutylketone, methyl isoamyl ketone, methyl n-amyl ketone and cyclohexanone;alkyl esters such as methyl acetate, ethyl acetate, isopropyl acetate,butyl acetate, ethyl formate, methyl propionate, methoxy propylacetateand ethyl butyrate; glycols and glycol esters and ethers, such asethylene glycol, 2-ethoxyethanol, 3-methoxypropylpropanol,3-ethoxypropylpropanol, 2-butoxyethyl acetate, 3-methoxypropyl acetate,3-ethoxypropyl acetate and 2-ethoxyethyl acetate; alkanols such asmethanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol anddialkyl and cyclic ethers such as diethyl ether and tetrahydrofuran.

The substantially non-polar, organic liquids which may be used, eitheralone or in admixture with the aforementioned polar solvents, arearomatic hydrocarbons, such as toluene and xylene, aliphatichydrocarbons such as hexane, heptane, octane, decane, petroliumdistillates such as white spirit, mineral oils, vegetable oils andhalogenated aliphatic and aromatic hydrocarbons, such astrichloro-ethylene, perchloroethylene and chlorobenzene.

Examples of suitable polar resins, as the medium for the dispersion formof the present invention, are film-forming resins such as are suitablefor the preparation of inks, paints and chips for use in variousapplications such as paints and inks. Examples of such resins includepolyamides, and cellulose ethers, such as ethyl cellulose and ethylhydroxyethyl cellulose. Examples of paint resins include short oilalkyd/melamine-formaldehyde, polyester/melamine-formaldehyde,thermosetting acrylic/melamine-formaldehyde, long oil alkyd andmulti-media resins such as acrylic, epoxy, polyurethane andurea/aldehyde.

The resin may also be an unsaturated polyester resin including theso-called sheet molding compounds and bulk molding compounds which maybe formulated with reinforcing fibres and fillers. Such moldingcompounds are described in DE 3,643,007 and the monograph by P. F.Bruins entitled “Unsaturated Polyester Technology”, Gordon and BreachScience publishers, 1976, pages 211 to 238.

If desired, the dispersions may contain other ingredients, for example,resins (where these do not already constitute the organic medium)binders, fluidizing agents (such as those described in GB-A-1508576 andGB-A-2108143), anti-sedimentation agents, plasticizers, levelling agentsand preservatives.

The composition of particulate solid, polyurethane dispersant, andoptional vehicle typically contains from 5 to 95% by weight of theparticulate solid, the precise quantity depending on the nature of thesolid and the relative densities of the solid and the organic medium.For example, a composition in which the solid is an organic material,such as an organic pigment, preferably contains from 15 to 60% by weightof the solid whereas a composition in which the solid is an inorganicmaterial, such as an inorganic pigment, filler or extender, preferablycontains from 40 to 90% by weight of the solid based on the total weightof composition.

The composition is preferably prepared by milling the particulate solidin the organic medium at a temperature which is not greater than 40° C.and especially not greater than 30° C. However, when the solid is acrude phthalocyanine pigment such as copper phthalocyanine, it issometimes preferable to carry out the milling in an organic liquid at atemperature between 50 and 150° C. since greener and brighter shades maybe obtained. This is particularly the case where the organic liquid is ahigh boiling aliphatic and/or aromatic distillate.

The composition may be obtained by any of the conventional methods knownfor preparing dispersions. Thus, the solid, the organic medium and thedispersant may be mixed in any order, the mixture then being subjectedto a mechanical treatment to reduce the particles of the solid to anappropriate size, for example, by ball milling, bead milling, gravelmilling, nano-milling, or plastic milling until the dispersion isformed. Alternatively, the solid may be treated to reduce its particlesize independently or in admixture with either the organic medium or thedispersant, the other ingredient or ingredients then being added and themixture being agitated to provide the dispersion.

If the composition is required in dry form, the liquid medium ispreferably volatile so that it may be readily removed from theparticulate solid by a simple separation means such as evaporation. Itis preferred, however, that the composition comprises the liquid medium.

If the dry composition consists essentially of the dispersant and theparticulate solid, it preferably contains at least 0.2%, more preferablyat least 0.5% and especially at least 1.0% dispersant based on weight ofthe particulate solid. Preferably the dry composition contains notgreater than 100%, preferably not greater than 50%, more preferably notgreater than 20%, and especially not greater than 10% by weightdispersant based on the weight of the particulate solid.

As described hereinbefore, the compositions are particularly suitablefor preparing millbases where the particulate solid is milled in aliquid medium in the presence of both a particulate solid and afilm-forming resin binder.

Thus, according to a still further aspect of the invention there isprovided a millbase comprising a particulate solid, dispersant and afilm-forming resin.

Typically, the millbase contains from 20 to 70% by weight particulatesolid based on the total weight of the millbase. Preferably, theparticulate solid is not less than 30 and especially not less than 50%by weight of the millbase.

The amount of resin in the millbase can vary over wide limits but ispreferably not less than 10%, and especially not less than 20% by weightof the continuous/liquid phase of the millbase. Preferably, the amountof resin is not greater than 50% and especially not greater than 40% byweight of the continuous/liquid phase of the millbase.

In embodiment, 1 preferably component (a) is a diisocyanate or mixturesof diisocyanates such as toluene diisocyanate (TDI), isophoronediisocyanate (IPDI), hexanediisocyanate (HDI), α,α-tetramethylxylenediisocyanate (TMXDI), diphenylmethane-4,4′-diisocyanate (4,4′-MDI),diphenylmethane-2,4′-diisocyanate (2,4′-MDI) anddicyclohexylmethane-4,4′-diisocyanate (HMDI). Preferably, component (a)is either TDI or IPDI or MDI.

The compound having a polyether chain which is component (b) ispreferably poly(C₂₋₃-alkylene oxide) which contains less than 60%poly(ethylene oxide) and also preferably contains two groups which reactwith isocyanates. Preferably, the amount of ethylene oxide is less than40% and especially less than 20% by weight of the poly(C₂₋₃-alkyleneoxide) chain. There are a number of ways of incorporating a polyetherlateral chain into an organic compound which contains these groups whichreact with isocyanates.

Thus, in the case where the two groups which react with isocyanates areboth hydroxyl, a poly(C₂₋₄-alkylene oxide) chain may be convenientlyattached by isocyanates having a functionality of two or more. Compoundsof this type are described in U.S. Pat. No. 4,794,147, which involvessequentially reacting a mono-functional polyether with a polyisocyanateto produce a partially capped isocyanate intermediate and reacting theintermediate with a compound having at least one active amino hydrogenand at least two active hydroxyl groups.

One preferred class of compound of this type may be presented by theformula 1.

wherein

R is C₁₋₂₀-hydrocarbyl group;

R¹ is hydrogen, methyl or ethyl of which less than 60% is hydrogen;

R² and R³ are each, independently, C₁₋₈-hydroxyalkyl;

Z is C₂₋₄-alkylene;

X is —O— or —NH—;

Y is the residue of a polyisocyanate;

m is from 2 to 150 and more preferably from 5 to 150;

p is from 1 to 4; and

q is 1 or 2.

R may be alkyl, aralkyl, cycloalkyl or aryl.

When R is aralkyl, it is preferably benzyl or 2-phenylethyl.

When R is cycloalkyl it is preferably C₃₋₈-cycloalkyl such ascyclohexyl.

When R is aryl it is preferably naphthyl or phenyl.

When R is alkyl, it may be linear or branched and preferably containsnot greater than 12, more preferably not greater than 8 and especiallynot greater than 4 carbon atoms. It is especially preferred that R ismethyl or butyl.

The C₂₋₄-alkylene radical represented by Z may be ethylene,trimethylene, 1,2-propylene or butylene.

Preferably m is not less than 10. It is also preferred that m is notgreater than 100 and especially not greater than 80.

When q is 2 it is possible to link two different polyurethane polymerchains but it is much preferred that q is 1.

When the polyisocyanate has a functionality which is greater than 2, thecompound which is component (b) may carry more than one poly (alkyleneoxide) chain. However, it is much preferred that p is 1, q is 1 and thatY is the residue of a diisocyanate.

When R¹ is a mixture of hydrogen and methyl and Z is 1,2-propylene and Xis —NH— the compound of formula 1 is a derivative of polyalkylene glycolamine such as a Jeffamine™ M polyether available from HuntsmanCorporation.

Preferably, R² and R³ are both 2-hydroxyethyl.

It is also preferred that X is O.

Compounds of formula 1 are typically prepared by reacting amono-functional polyether with a polyisocyanate in an inert solvent suchas toluene at a temperature of from 50 to 100° C. until the desiredisocyanate value is reached optionally in the presence of an acidcatalyst. In one embodiment the acid catalyst is present and in anotherembodiment the acid catalyst is absent. The temperature is then normallyreduced to between 40 and 60° C. when the requisite secondary amine suchas diethanolamine is added.

Useful compounds of formula 1, have been used as component (b) byreacting a poly (propylene glycol) mono methyl ether, a poly (propyleneglycol) mono butyl ether or a Jeffamine™ M series polyether having anumber average molecular weight of from 250 to 5,000 with a diisocyanatesuch as TDI followed by diethanolamine.

A second preferred type of compound which can be used as component (b)is of formula 2.

wherein

R, R¹, Z and m are as defined hereinbefore;

R⁴ is an isocyanate reactive organic radical (group);

R⁵ is hydrogen or an isocyanate-reactive organic radical; and

n is 0 or 1.

The organic radical represented by R⁴ and R⁵ is an organic radicalcontaining an isocyanate-reactive group, such as —OH, —SH, —COOH, —PO₃H₂and —NHR⁶ in which R⁶ is hydrogen or optionally substituted alkyl. Asspecific examples of isocyanate-reactive radicals, there may bementioned hydroxyalkyl, hydroxy alkoxy alkyl, hydroxy (poly alkyleneoxy) alkyl and hydroxy alkoxy carbonyl alkyl.

A preferred type of compound of formula 2 is where n is zero, Z is1,2-propylene, R⁴ is —CH₂CH₂C(O)—O-(L)_(q′)—H. Wherein L is ahydrocarbyl group or alkoxy group, preferably L is a C₂ to C₃hydrocarbyl group or alkoxy group; and q′ is 1 to 20, preferably 1 to 6and most preferably 1. R⁵ is hydrogen. Compounds of this type areobtainable or obtained by the Michael addition reaction of a poly(alkylene oxide) monoalkyl ether monoamine and a hydroxy functionalacrylate such as 2-hydroxyethyl acrylate or hydroxypropyl acrylate. Asuitable source of poly (alkylene oxide) monoalkyl ether monoamine isthe Jeffamine™ M series of polyethers available from HuntsmanCorporation. The reaction between the poly (alkylene oxide) monoalkylether monoamine and 2-hydroxy functional acrylate is typicallycarried out in the presence of air and at a temperature of 50 to 100°C., optionally in the presence of a polymerization inhibitor such ashydroquinone or butylated hydroxy toluene.

Another preferred type of compound of formula 2 is where n is zero, Z is1,2-propylene and R⁴ and R⁵ are both 2-hydroxyethyl. Compounds of thistype may be prepared by reacting a poly(alkylene oxide) mono alkyl ethermono amine with ethylene oxide under acidic conditions.

Yet another preferred type of compound of formula 2 is where n is zero,Z is 1,2-propylene and R⁴ is —CH₂CH₂C(O)—O-(L)_(q′)—H and R⁵ ishydrogen. Wherein L is a hydrocarbyl group or alkoxy group, preferably Lis a C₂ to C₃ hydrocarbyl group or alkoxy group; and q′ is 1 to 20,preferably 1 to 6 and most preferably 1. R⁵ is hydrogen. Compounds ofthis type may be prepared by reacting a poly(alkylene oxide) mono alkylether mono amine with about one stoichiometric equivalent of ethyleneoxide under acidic conditions.

Poly (alkylene oxide) monoalkyl ether monoamines may also be obtainedfrom reaction of a poly (alkylene oxide) monoalkyl ether withacrylonitrile and hydrogen reduction according to the following generalscheme where R and R¹ are as previously described.

A further preferred type of compound of formula 2 where n is zero, Z is1,3-propylene and R⁴ is 2-hydroxyethyl and R⁵ is hydrogen may beobtained from reaction between poly (alkylene oxide) monoalkyl ethermonoamines of formula 2A and a hydroxy functional acrylate such as2-hydroxyethyl acrylate or hydroxypropyl acrylate.

A third preferred type of compound which may be used as component (b) isof formula 3:

wherein R, R¹ and m are as defined hereinbefore and W is C₂₋₆-alkyleneand especially ethylene. Compounds of this type are obtainable orobtained by the Michael addition reaction of a hydroxy amine and a poly(alkylene oxide) acrylate.

A fourth preferred type of compound which may be used as component (b)is of formula 4.

wherein

R, R¹, Z, m and n are as defined hereinbefore;

R⁷ represents hydrogen, halogen or C₁₋₄ alkyl;

Q is a divalent electron withdrawing group; and

T is a divalent hydrocarbon radical which may carry substituents orcontain hetero atoms.

Examples of electron withdrawing groups which may be represented by Qinclude —CO—, —COO—, —SO—, —SO₂—, —SO₂O— and —CONR⁸— in which R⁸ ishydrogen or alkyl.

Hydrocarbon radicals which may be represented by T include alkylene,arylene and mixtures thereof, said radicals optionally carryingsubstituents or containing hetero-atoms. Examples of suitable radicalsrepresented by T are alkylene radicals containing from 1 to 12 carbonatoms, oxyalkylene and polyoxyalkylene radicals of the formula—(CH₂CH(R¹)O)x wherein R¹ is as defined hereinbefore and x is from 1 to10,

phenylene and diphenylene radicals and other arylene radicals such as

wherein Y′ is —O—, —S—, —CH₂—, —CO— or —SO₂—

The compounds of Formula 4 are obtainable or obtained by the Michaeladdition reaction of two moles of a poly (alkylene oxide) monoalkylether monoamine with one mole of an unsaturated compound of the formula5.

wherein Q, T and R⁷ are as defined hereinbefore.

Examples of unsaturated compounds of Formula 5 are especiallydiacrylates and dimethacrylates wherein T is a C₄₋₁₀-alkylene residue, apolyoxyalkylene residue or an oxyethylated Bisphenol A residue.

When component (b) is a polyester containing two groups which react withisocyanates the polyester chain may be made by polymerizing one or morehydroxy carboxylic acids or lactones thereof in the presence of either ahydroxy or carboxy containing compound which acts as a polymerizationterminating moiety.

The polyester obtained using a hydroxy containing compound as chainterminating compound is preferably of formula 6.R⁹O(OC-A-O)_(m′)H  6

wherein

m′ is from 2 to 150 and more desirably from 5 to 150;

R⁹ is C₁₋₅₀-hydrocarbyl group; and

A is C₁₋₂₆-alkylene and/or C₂₋₂₆-alkenylene.

The polyester obtained using a carboxylic containing compound as chainterminating compound is preferably of formula 7.R⁹CO(O-A-CO)_(m′)OH  7

wherein

R⁹, A and m′ are defined hereinbefore.

The polyester of Formulae 6 and/or 7 are typically made by reacting oneor more hydroxy carboxylic acids together with either a hydroxycontaining compound or carboxy containing compound at 50 to 250° C. inan inert atmosphere and in the presence of an esterification catalyst.Typical process conditions are described in WO 01/80987.

Compounds of Formula 6 may be reacted with a polyisocyanate and asecondary amine under similar conditions described for the preparationof compounds of Formula 1 to form polyester analogues.

Compounds of Formula 7 may be converted to a mono hydroxy compound byreacting with a diol such as ethylene glycol or propylene glycol and theresulting mono hydroxy derivative treated in similar manner to thecompound of Formula 6 in preparing polyester analogues to the polyetherof Formula 1.

A polyester which contains 2 functional groups which are reactivetowards an isocyanate at one end of the polyester may be prepared by theMichael addition of an aminoalcohol with a polyester acrylate such as apolycaprolactone acrylate with ethanolamine.

When component (b) is a compound which contains a poly(alk)acrylatechain, it is preferably a poly(meth)acrylate containing either twohydroxyl groups at one end of the acrylate chain or one hydroxyl and oneimino group at one end of the acrylate chain. The two hydroxyl groups orthe one hydroxyl and one imino group are preferably separated by 1 to 6carbon atoms. Polyacrylates of this type are obtainable or obtained byreacting a diol with an acrylate by, for example, Atom Transfer RadicalPolymerization as illustrated by the following reaction scheme.Reactions of this type are disclosed in Macromolecules 1995, 28, 1721and 1997, 30, 2190 and in J. Am. Chem. Soc. 1995, 117, 5614.

wherein R¹⁰ is C₁₋₂₀-hydrocarbyl group and in is as defined hereinbeforee.g. from 2 to 150 and more desirably from 5 to 150.

Alternatively, a dihydroxy functional poly(alk)acrylate may be preparedby the free radical polymerization of a (meth)acrylate monomer(s) in thepresence of a dihydroxy functional chain transfer agent such asthioglycerol according to the following reaction scheme.

The reaction is preferably carried out in the presence of an initiatorsuch as azo bis-(isobutyronitrile) (AIBN).

wherein R¹⁰ and in are as defined hereinbefore.

Monohydroxy functional polymer chains (polyether, polyester orpoly(alk)acrylate) may be converted to polymer chains containing both ahydroxyl and imino group at one end by first reaction with an isocyanatefunctional acrylate followed by a Michael addition of an alkanolamine tothe resulting adduct.

The following scheme illustrates such a synthetic conversion startingwith a monohydroxy functional polyester.

wherein R¹⁰ and m are as defined hereinbefore.

When component (b) is a compound which contains a polyolefin chain, itis preferably a polyolefin containing either two hydroxyl groups at oneend of the polyolefin chain or one hydroxyl and one imino group at oneend of the polyolefin chain. It is preferred that the polyolefin chainis polyisobutylene. Polyisobutylene chains which contain 2 or moreisocyanate reactive groups at one end of the chain may be prepared frompolyisobutenyl succinic anhydride (PIBSA). Reaction of PIBSA with analkyl diamine yields a polyisobutylene with a primary amine on one end.This is illustrated for one type of PIBSA.

The primary amine ended polyisobutylene chain may be converted to yielda product with two isocyanate reactive groups by Michael addition of ahydroxy functional acrylate or addition of ethylene oxide in ananalogous way to that described above for poly (alkylene oxide)monoalkyl ether monoamines.

As disclosed hereinbefore component (c) is a compound containing an acidor amine group and at least two groups which react with isocyanates.Preferably, the compound contains only two groups which react withisocyanates since this restricts cross-linking between adjacent chainsof the dispersant. The acid group may be phosphonic, sulphonic orpreferably carboxylic, including mixtures thereof. Preferably, thegroups of component (c) which react with isocyanates are both hydroxygroups. A preferred diol which is component (a) is a compound of formula8.

wherein at least two of the groups R¹¹, R¹² and R¹³ are C₁₋₆-hydroxyalkyl and the remainder is C₁₋₆-hydrocarbyl group, which may be linearor branched alkyl, aryl, aralkyl or cycloalkyl, M is hydrogen or analkaline metal cation, or quaternary ammonium cation. Preferred examplesof carboxylic acid components are dimethylolpropionic acid (DMPA) anddimethylolbutyric acid (DMBA).

The acid containing compound which is component (c) may contain otheracid groups in addition to or instead of a carboxylic group(s), such asphosphonic or sulphonic acid groups. An example of one such compound is1,3-benzene dicarboxylic acid-5-sulpho-1,3-bis(2-hydroxyethyl) ester(EGSSIPA).

When component (c) carries a basic group in addition to the two groupswhich react with isocyanates it is essential that the basic group doesnot react with isocyanates. Basic groups of this type are aliphatictertiary amines, hindered aromatic amines and nitrogen heterocycliccompounds which may be alicyclic or aromatic. Examples of hinderedaromatic amines are phenylamines having a steric hindering group in the2 and/or 6-position. In one embodiment, it is desirable that thedispersant comprise a nitrogen in a non-reactive amine (non-reactivewith respect to isocyanates) laterally attached to the polyurethanebackbone such that said nitrogen atom is separated by at least two atomsfrom the closest atom on the backbone. Such non-reactive amineslaterally attached are thought to provide better anchoring to someparticulate solids. The non-reactive amine preferably is a tertiaryamine. The non-reactive amine may also be a quaternary ammonium salt.Specific examples of component (c) having a basic group are N-methyldiethanolamine (NMDA), N-phenyldiethanolanine (NPDA),N,N-bis(2-hydroxyethyl)isonicotinamide (HEINA),1,1′-{[3-(dimethylamino)-propyl]imino}bis-2-propanol and compound 9formed from the Michael addition of dimethylaminopropylamine and2-hydroxyethyl acrylate.

The formative compounds which are component (d) of the polyurethane arepreferably difunctional in respect of reactivity with isocyanates forembodiment 1 although a small amount of higher functionality may be usedwhere a small amount of branching of the polyurethane polymer backboneis desired. However, it is preferred that component (d) is difunctional.Preferred reactive groups are amino and hydroxy and it is much preferredthat component (d) is a diamine or especially a diol. Component (d), ifpresent, is used primarily as a chain extender to alter the solubilityof the polyurethane polymer.

Examples of suitable diamines are ethylene diamine, 1,4-butane diamineand 1,6-hexane diamine.

Examples of suitable diols are 1,6-hexanediol, 1,4-cyclohexanedimethanol(CHDM), 1,2-dodecanediol, 2-phenyl-1,2-propanediol, 1,4-benzenedimethanol, 1,4-butanediol and neopentyl glycol. The diol may also be apolyether such as a poly (C₂₋₄-alkylene glycol), a polyester orpolyacrylic diol. The polyalkylene glycol may be a random or block(co)polymer containing repeat ethyleneoxy, propyleneoxy or butyleneoxygroups, including mixtures thereof.

As noted hereinbefore, it is preferred that the polyurethane polymerbackbone in embodiment 1 is essentially linear in character. However,some small amount of branching may be unavoidable if there is a presenceof polyols or polyisocyantes with a functionality higher than 2 presentas an impurity in any of the components. The higher functionalitypolyols or polyisocyanates are preferred in both embodiments 2 and 3.

As disclosed hereinbefore the chain terminating compound which iscomponent (e) is mono-functional with respect to the isocyanate. Themonofunctional group is preferably an amino or hydroxy group. Preferredterminating groups are solubilizing poly (C₂₋₄-alkylene) mono alkylethers, poly (C₂₋₄-alkylene) mono alkyl ether amines, polyesters,polyacrylates and polyolefins similar to those used in the preparationof the lateral side chain compounds which are component (b) of thepolyurethane.

An example of a monoisocyanate which acts as a chain terminatingcompound (component f) is phenyl isocyanate. An example of amonoisocyanate which contains a carbon to carbon double bond is2-isocyanatoethyl methacrylate.

It is much preferred that the amount of component (f) is zero.

Typical amounts of the aforementioned compounds from which thepolyurethane polymers are obtainable are 15-50% component (a), 10-80%component (b), 0-24% component (c), 0-25% component (d), 0-50% component(e) and 0-20% component (f), all based on the total weight of thepolyurethane polymer.

When component (e) is a monofunctional polyether, polyester,poly(alk)acrylate or polyolefin the total amount of component (b) withcomponent (e) is preferably not less than 35% and where component (e) isother than a monofunctional polyether, polyester or poly(alk)acrylatethe amount of component (b) is preferably not less than 35%.

Alternatively, the ratio of total number of isocyanate groups providedby component (a) and optionally component (f) is greater that the totalnumber of isocyanate reactive groups provided by component (b) andcomponents (c), (d) and (e) when present. The resultant polyurethane isthen a prepolymer containing residual isocyanate functionality. Thisprepolymer may then be reacted with other chain extenders such ascomponent (d) which conjoins different prepolymer chains and/or withchain terminating compounds which are component (e), optionally prior toor during dissolution in water or other polar solvent. In one embodimentprepolymer is reacted with chain extenders prior to dissolution solvent.In one embodiment prepolymer is reacted with chain extenders duringdissolution in solvent. In one embodiment prepolymer is reacted withchain extenders prior to dissolution in the absence of water or othersolvent. In one embodiment the prepolymer may be reacted with chainextenders in the absence of water.

The preparation of prepolymers can be useful since it is a means ofcontrolling viscosity during the preparation of the polyurethanepolymer, especially in circumstances where the reaction is carried outin the absence of any solvent.

When a prepolymer is formed which contains isocyanate functionality,chain extension may be carried out by water itself, or a polyol,amino-alcohol, a primary or secondary aliphatic, alicyclic, aromatic,araliphatic or heterocyclic polyamine especially a diamine, hydrazine ora substituted hydrazine. This type of reaction is used moresignificantly in embodiment 3.

Examples of suitable chain extenders include ethylenediamine, diethylenetriamine, triethylene tetramine, propylenediamine, butylenediamine,hexamethylenediamine, cyclohexylenediamine, piperazine, 2-methylpiperazine, phenylenediamine, tolylene diamine, xylylene diamine,tris(2-aminoethy)amine, 3,3′-dinitrobenzidine,4,4′methylenebis(2-chloraniline), 3,3′-dichloro-4,4′bi-phenyl diamine,2,6-diaminopyridine, 4,4′-diaminodiphenylmethane, methane diamine,m-xylene diamine, isophorone diamine, and adducts of diethylene triaminewith acrylate or its hydrolyzed products. Also materials such ashydrazine, azines such as acetone azine, substituted hydrazines such as,for example, dimethyl hydrazine, 1,6-hexamethylene-bis-hydrazine,carbodihydrazine, hydrazides of dicarboxylic acids and sulphonic acidsuch as adipic acid mono- or dihydrazide, xalic acid dihydrazide,isophthalic acid dihydrazide, tartaric acid dihydrazide, 1,3-phenylenedisulphonic acid dihydrazide, omega-aminocaproic acid dihydrazide,hydrazides made by reacting lactones with hydrazide such asgamma-hydroxylbutyric hydrazide, bis-semi-carbazide carbonic esters ofglycols such as any of the glycols mentioned above. Hexamethylenediamineis especially preferred.

The chain extension can be conducted at elevated, reduced or ambienttemperatures. Convenient temperatures are from about 5° C. to 95° C.

When employing a prepolymer in the preparation of the polyurethanepolymer, the amount of chain extender and chain terminating compound arechosen to control the molecular weight of the polyurethane polymer. Ahigh molecular weight will be favoured when the number ofisocyanate-reactive groups in the chain extender is approximatelyequivalent to the number of free isocyanate groups in the prepolymer. Alower molecular weight of the polyurethane polymer is favoured by usinga combination of chain extender and chain terminator in the reactionwith the polyurethane prepolymer.

An inert solvent may be added before, during or after formation of thepolyurethane polymer/prepolymer in order to control viscosity. Examplesof suitable solvents are acetone, methylethylketone, dimethylformamide,dimethylacetamide, diglyme, N-methylpyrrolidone, butylacetate,methoxypropyl acetate, ethylacetate, ethylene and propyleneglycoldiacetates, alkyl ethers of ethylene and propylene glycolacetates, toluene, xylene and sterically hindered alcohols such ast-butanol and diacetone alcohol. Preferred solvents are ethyl acetate,butyl acetate, methoxy propylacetate and N-methylpyrrolidone. Thepolyurethane may also be formed in the presence of unsaturated monomerswhich include mono functional and polyfunctional (meth)acrylates andstyrenic monomers.

The number average molecular weight of the polyurethane polymer ispreferably not less than 2,000, more preferably not less than 3,000 andespecially not less than 4,000. It is also preferred that the numberaverage molecular weight of the polyurethane polymer is not greater than50,000, more preferably not greater than 30,000 and especially notgreater than 20,000.

It is preferred for embodiment 1 and subsequent embodiments that theamount of residual isocyanate functionality in the dispersant is lessthan 0.1% and more preferably about zero.

Embodiment 2

According to the invention, there is provided a non-aqueous compositioncomprising a particulate solid, an organic medium and a polyurethanedispersant having an essentially non-linear backbone with laterally andor terminally attached solvent-solubilizing side chains of a polyester,a polyacrylic, a polyether or a polyolefin including mixtures of suchside chains. The polyurethane dispersant is further characterized inthat it also comprises groups containing carbon carbon double bonds inthe same amounts as in embodiment 1. Similar to embodiment 1 subsequentto polyurethane dispersant formation the double bonds may be reactedwith a crosslinking agent added to the composition to crosslink (orchain extend) the dispersant around the particle surface. Alternatively,the double bonds may be used to bond the dispersant to a continuousphase in a molding composition, coating, or ink that containsco-reactive continuous phase.

Embodiment 2 differs from embodiment 1 in that a small amount oftrifunctional or higher monomer in the urethane forming reactions areused. This generates some branch points in the polyurethane backbone.The trifunctional or higher reactants can be polyols, polyamines, orpolyisocyanates. For embodiment 2 it is preferred that the higherfunctional reactants are polyols or polyamines. It is especiallypreferred that they are polyols.

In embodiment 2, the proportions of mono, di and higher functionalcomponents in the polyurethane synthesis are chosen such that a branchedpolyurethane is produced as opposed to a fully crosslinked gel. It ispreferred that the number average molecular weight of the polyurethaneis not greater than 100,000. It is more preferred number averagemolecular weight of the polyurethane is not greater than 70,000 andespecially not greater than 40,000. It is preferred that the numberaverage molecular weight of the polyurethane is at least 3,000. It ismore preferred number average molecular weight of the polyurethane is atleast 5,000 and especially at least 7,000. It is preferred that theaverage number of branch points in the polyurethane is at least 1. It ismore preferred that the average number of branch points in thepolyurethane is at least 2 and especially at least 3. It is alsopreferred that the average number of branch points in the polyurethaneis not greater than 20. It is more preferred that the average number ofbranch points in the polyurethane is not greater 12 and especially notgreater 8. (The average number of branch points in the polyurethane maybe calculated from the molar proportions of mono, di and higherfunctional compounds used to prepare the polyurethane).

Embodiment 2 can be made according to the same general procedure forforming embodiment 1 from components a-f with the followingsubstitutions.

For the (a) component (polyisocyanates), the functionality can be fromabout 2 to about 10 (on average) and in one aspect from about 2 to about6. The additional isocyanates with functionality from about 2.5 to about6 or 10 are well known materials and more fully described in U.S. Pat.No. 6,509,409 column 4, line 8, through column 7, line 18. Theisocyanates may be blends of different isocyanates or reaction productsof excess equivalents of isocyanates with polyols or polyamines to formpolyfunctional isocyanates. It is preferred that the averagefunctionality of polyisocyanate is from 2.0 to 2.5. It is more preferredthat the average functionality of polyisocyanate is from 2.0 to 2.2. Itis especially preferred that the average functionality of polyisocyanateis about 2.0.

In embodiment 2, the presence of component (b), the lateral solubilizingchains, is optional. It was considered essential in some aspects of theinvention to have lateral side chain solubilizing groups to get thesufficient solubilizing chains in the dispersant.

It is preferred that one or more formative compounds (d) are present.For the formative compounds of component (d), it is preferred that theaverage number of groups that react with isocyanates is greater than2.0, more preferred greater than 2.05 and especially greater than 2.1.It is preferred that the average number of groups that react withisocyanates is not more than 3.0. It is more preferred that that theaverage number of groups that react with isocyanates is not more than2.6 and especially not greater than 2.4.

At least one of the components (a) or (d) must have an averagefunctionality greater than 2.0.

The isocyanates of embodiment 2 can be prereacted with any of the othercomponents (such as a mono-functional or difunctionalsolvent-solubilizing component) as there are generally less restrictionson reaction conditions with components having a functionality above 2.

Embodiment 2 may look like the structure below which schematicallydepicts a polyurethane wherein terminal solubilizing chains are presentwith six branch points.

Embodiment 3

The polyurethane dispersants disclosed by Byk (U.S. Pat. Nos. 4,647,647;4,795,796; 4,942,213; and EP 154,678), Efka (U.S. Pat. Nos. 5,399,294;5,425,900; and 5,882,393) and Avecia U.S. Pat. No. 6,509,409 can also bemodified to include carbon to carbon double bonds in the same amounts asembodiment 1 using the same reactants of embodiments 1 and 2 andoptionally a slightly different reaction procedure. The startingmaterials for embodiment 3 include the starting materials fromembodiments 1 and 2 along with the use of proportionately more urethaneforming monomers of higher than 2 functionality. The isocyanates (“a”)in embodiment 3 are the same as in embodiment 2, and typically inembodiment 3 the isocyanates on average have higher functionality than2. The compounds “b” of embodiment 3 are usually absent (meaning thereis usually monofunctional solvent-solubilizing chains from component(e)) The remainder of the components are very similar/interchangeable.

The polyurethane dispersants from Byk and Efka are characterized in thatthey are made with polyisocyanates. For Byk patents functionality of thepolyisocyanate is ≧2.5 for Efka >2. Monofunctional solvent solubilizingchains are on average a little less expensive than difunctionalsolubilizing chains. The polyurethanes of embodiment 3 are prepared in a3 stage process.

Stage 1

A portion of the isocyanate groups of the isocyanate component “a” arereacted with a polymer chain (polyester, polyether, polyacrylate orpolyolefin) which contains one group which reacts with isocyanates (thesolvent solubilizing chain of the dispersant) component (e).

Stage 2

A further portion of the isocyanate groups are reacted with material(s)which contain 2 or more groups that react with isocyanates (component“d”) e.g. a diol such as a PEG. This serves to link together several ofthe polyisocyanate derivatives to build molecular weight. Optionally acompound having an amino group (component “c”) or a chain terminator(component “e”) may be added at this stage. Any of components b-f maycontain carbon to carbon double bonds.

Stage 3

The residual isocyanates (if present) can then be reacted e.g. withmaterials such as e and f of embodiments 1 and 2 which aremonofunctional with respect to reactivity with isocyanate to introduceother functional groups e.g., tertiary or aromatic amines as in U.S.Pat. No. 4,647,647.

Incorporation of carbon to carbon double bonds may be achieved by either

(i) incorporating the double bond in the solvent solubilizing chainintroduced in stage 1 e.g. using a polymeric chain (e.g. polylactone)with a hydroxy group at one end and an acrylate at the other, or

(ii) Incorporating the carbon to carbon double bond using a monofunctional material with respect of isocyanate reactive groups (such asa hydroxyl functional acrylic monomer like hydroxyethyl acrylate) suchthat the double bond is closer to the anchoring core.

If a primary or secondary amine functional material is absent in stage3, it would be possible to add the hydroxy functional acrylate (orsimilar) at any stage. However, if you do use such an amine the acrylatewill have to be added last to prevent reaction between the amine and theactivated double bond.

The invention thus relates to addition compounds or their salts suitableas dispersing agents which contain reactive carbon carbon double bonds.Such compounds are obtainable by the reaction of polyisocyanates,hydroxyl compounds, compounds having Zerewitinoff-active hydrogen and atleast one basic group containing nitrogen, and optionally compoundscontaining amine hydrogen, optionally in the presence of solvents andoptionally in the presence of reaction catalysts, characterized in thatthey are obtainable by the reaction of polyisocyanates (a) having anaverage functionality of from 2.5 to 6 with monohydroxyl compounds (e)of the formula IY″—OH  Iwherein Y″ has the following meanings:(i) aliphatic and/or cycloaliphatic hydrocarbon groups with 8 to 30carbon atoms in which the hydrogen atoms may be partly replaced byhalogens and/or aryl groups, (ii) aliphatic, cycloaliphatic and/oraromatic groups with molecular weights of from 350 to 8000 which containat least one —O— and/or —COO— group and in which the hydrogen atoms maybe partly replaced by halogens.

Optionally, the group Y″ contains at least one carbon to carbon doublebond. Desirably from 15 to 50%, preferably 20 to 40% and most preferably20 to 35% of the NCO groups are reacted. Reacting the resulting reactionproduct in such a quantity with compounds (d) of the formula IIG-(E)_(n′)  IIwherein E stands for —OH, —CO₂H, —NH₂ and/or —NHR (wherein R representsan alkyl group having 1 to 4 carbon atoms) and n′ stands for 2 or 3, andG represents an aliphatic, cycloaliphatic and/or aromatic group withmolecular weights of at the most 3000 which has at least 2 carbon atomsand may contain —O—, —CONH—, —S— and/or —SO₂— groups, that a further 15to 45%, preferably 20 to 40% and most preferably 20 to 35% of the NCOgroups of the polyisocyanates originally put into the process arereacted but the sum of the degrees of NCO reaction of reactions (a) and(b) amounts to at least 40% and at the most 75%, preferably 45 to 65%and most preferably 45 to 55%.

Optionally, the group G contains at least one carbon to carbon doublebond (c) reacting the resulting reaction product in such a quantity withcompounds (e) of the general formula III & IVZ′-Q′  IIIT′-Q′  IVwherein Q′ stands for —OH, —NH₂, —NHR¹⁶ (wherein R¹⁶ stands for an alkylgroup having 1 to 4 carbon atoms) or —SH, and Z′ is an aliphatic groupwith 2 to 10 carbon atoms containing at least one tertiary amino groupor a heterocyclic group containing at least one basic ring nitrogen atomwhich carries no hydrogen atom, which heterocyclic group may be attachedto the group Q′ by way of an alkylene group having up to 10 carbonatoms, T′ is a group which contains at least one carbon to carbon doublebond, that at least one molecule of the compounds III and IV isavailable for each remaining isocyanate group which has not been reactedin stages (a) and (b). The amount of compound IV can vary from 0-100% ofthe amount needed to react with the remaining isocyanate groups.

Reaction with compounds III and IV may occur sequentially or together.However it is preferred that reaction of compound III occurs firstespecially if T′ contains an acrylate group and Q′ in compound III is—NH₂ or —NHR¹⁶.

It is necessary that at least one or more of the compounds I, II or IVcontain a carbon to carbon double bond.

The invention also relates to the process for the preparation of theaddition compounds as described above.

The invention further relates to the use of the addition compoundsdescribed above as dispersing agents.

Crosslinking the Dispersant for Encapsulation of Particle

The dispersant can be crosslinked or chain extended around theparticulate matter of the composition. The crosslinking or chainextension is achieved by addition of a crosslinking agent which containsfunctional groups which react with the double bonds contained within thedispersant or by an addition polymerization reaction of those doublebonds.

If a crosslinking agent is used, it may be added at any stage of thedispersion process, but it is preferred if it is added after theparticles have been dispersed in the liquid medium with the dispersantalready present. It is preferred that the average functionality of thecrosslinking agent is at least 2. It is especially preferred if theaverage functionality of crosslinking agent is 3 or more. It ispreferred that the crosslinking agent it comprises amine functionality(primary &/or secondary). It is preferred that the average functionalityof the total of primary and secondary amine groups in the crosslinker is2 or more. It is preferred that the crosslinker contains at least 2primary amine groups.

The amount of polyfunctional amine required in the composition willdepend on the amount of dispersant used and functionality of each withrespect to primary and secondary amine groups and reactive double bondsrespectively. It is preferred if the ratio of primary and secondaryamine groups to reactive double bonds is the range of 1 to 10 and 10to 1. It is more preferred if the range is 1 to 5 to 5 to 1. It isespecially preferred if the range is 1 to 3 to 3 to 1.

The polyfunctional amines for crosslinking can be from a wide variety ofmaterials and can be used as a single material or in mixtures of suchmaterials. They may be aliphatic or aromatic. There are numerousspecific examples. H₂N(CH₂)_(n″)NH₂ where n″=2 to 20, specific examplesinclude n″=2, n″=6, n″=12; H₂N(CH₂CH₂NH)_(m″)CH₂CH₂NH₂ where m″=1 to 10preferably 1 to 6; Spermidine, spermine;N,N′-bis(3-aminopropyl)-ethylenediamine;N,N′-bis(3-aminopropyl)-1,3-propanediamine; tris(2-aminoethyl)amine;4,4′-methylenebis(cyclohexylamine); diaminocyclohexane; 1 isophoronediamine; polyethyleneimine; Jeffamine D and T series polyether amines(supplied by Huntsman).

Cocure of the Dispersant with a Reactive Binder System

The dispersants may be used in a composition containing a reactivebinder system which contains unsaturation. The reactive binder is curedafter the addition of the dispersion containing the dispersant. Thereactive binder may be liquid as in the case of a 100% UV cure ink or itmay be solid for instance for a UV cure powder coating.

The cure may be brought about by generation of free radicals eitherthermally or from a radiation source. There are many initiators known tothose skilled in the art which can be used to generate radicals whensubjected to an increase in temperature. The choice of initiator isgoverned by the desired operating temperature, solubility, desired rateof cure etc. There are many examples of peroxides, hydroperoxides andazo compounds that can be used. The generation of radicals from“thermal” initiators can also be catalysed so that cure can take placeat ambient temperatures. One well known example is the use of tertiaryamines to catalyse the generation of radicals from peroxides. There arealso a wide range of initiators which may be used for UV cure. Thechoice among other factors will depend on the wavelength of radiationused.

The binder systems may vary greatly in composition. The system willcontain reactive unsaturation with which the carbon to carbon doublebonds in the dispersant will coreact. These reactive groups may bepresent on monomeric, oligomeric and/or polymeric components in thereactive binder system. The types of reactive double bonds in the bindermay be drawn from acrylate, methacrylate, or styrenic. It will be usualthat the reactive binder systems will contain a portion of materialwhich contains a reactive functionality of >2 to enable formation of across linked network.

There are a very wide range of monomers and oligomers available withmono, di and polyfuntionality of reactive double bonds. The oligomersinclude unsaturated polyesters, epoxy acrylates, urethane acrylates,polyester acrylates, polyether acrylates and acrylated acrylics.

The monofunctional monomers include alkyl acrylates, methacrylates, andstyrene. Difunctional monomers include the following acrylate functionalmonomers and their methacrylate equivalents-1,6-hexanediol diacrylate,1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, cyclohexanedimethanol diacrylate, diethylene glycol diacrylate, dipropylene glycoldiacrylate, ethoxylated bisphenol A diacrylate, and neopentyl glycoldiacrylate. Polyfunctional monomers include the following acrylatefunctional monomers and their methacrylateequivalents—trimethylolpropane triacrylate, pentaerythritol triacrylate,pentaerythritol tetracrylate, and di-trimethylolpropane tetraacrylate.

In sheet and bulk molding compounds, the most common type of reactivebinder systems are unsaturated polyester in combination with styrenemonomer. The binder is formulated with other components well known tothose skilled in the art such as fibres, release agents. Therefore,co-reactivity of the carbon to carbon double bond in the dispersant withstyrene is essential for use in these systems.

For reactive curing systems it is particularly desirable to minimize theVOC content of the final formulation. Therefore, it is preferable forthe dispersants to be delivered either in a minimum of organic solvent,as 100% active, or dissolved in a reactive component of the curingsystem.

Preparation of Intermediates

The preparation of the intermediates and dispersants described below wascarried out on more than one occasion. Some intermediate preparationswere repeated to provide more material for testing.

Intermediate A—Dihydroxy Polyester

1-Dodecanol (32.1 parts, 0.0.172 mol), ε-caprolactone (186.76 parts,1.631 mol) and δ-valerolactone (60.35 parts, 0.603 mol) were stirredtogether under nitrogen at 180° C. Zirconium butoxide catalyst (1.34parts) was added and the reactants were stirred under nitrogen for ca.20 hours at 180° C. After cooling to 20° C., the polyester was obtainedas a waxy solid. This is polyester 1.

Tolylene diisocyanate (26.88 parts,) was added to a reaction vessel withmethoxypropyl acetate (100 parts) heated to 40° C. Polyester 1 (250parts) dissolved in methoxypropyl acetate (100 parts) was added over 2hours with stirring at 50-60° C. The reaction was monitored using onlineinfrared detection. Reaction was continued at 60° C. for a further 30minutes after the end of the feed. The temperature was raised to 70° C.and reaction continued for a further 1 hour. At this stage the infraredpeak associated with the NCO group was showing no further decrease insize. The reactants were then cooled to 7° C. with an external ice bathand a solution of diethanolamine (16.22 parts) in methoxypropyl acetate(32 parts) was added causing a temperature rise to 21° C. The reactionwas continued with stirring at 35° C. until no isocyanate remained.

Intermediate B—Hydroxyamino PO Polyether

Jeffamine M2005 (8000 parts), 2-hydroxyethyl acrylate (456.4 parts) and2,6-di-tert-butyl-4-methyl phenol (2.72 parts) were stirred together for48 hours at 70° C. until the Michael addition reaction was complete.

Intermediate C

1-Dodecanol (93.15 parts), ε-caprolactone (399.5 parts) andδ-valerolactone (350.4 parts) were stirred together under nitrogen at150° C. Zirconium butoxide catalyst (4.0 parts) was added and thereactants were stirred under nitrogen for 20 hours at 180° C. Aftercooling to 20° C., the polyester obtained was a viscous liquid. This ispolyester 2.

Tolylene diisocyanate (82.63 parts) was added to a reaction vessel andheated to 50° C. under nitrogen. Polyester 2 (800 parts) was added over2 hrs with agitation at 50-60° C. The reaction was continued withstirring at 60° C. for 1 hour. The reactants were then cooled to 20° C.and diethanolamine (49.88 parts) was added. The reaction was continuedwith stirring at 35° C. until no isocyanate remained.

Intermediate D

Hydroxyethyl methacrylate (80.0 parts), ε-caprolactone (666.73 parts)and δ-valerolactone (215.44 parts), 4-methoxy phenol (0.96 parts),tin(II) chloride (0.05 parts) were stirred together under an airatmosphere at 125° C. The reaction was allowed to continue at thistemperature for 20 hours. After cooling to 20° C., the polyester wasobtained as a waxy solid.

Intermediate E

1-Dodecanol (114.16 parts), ε-caprolactone (666.73 parts) andδ-valerolactone (215.44 parts) were stirred together under nitrogen at150° C. Zirconium butoxide catalyst (4.0 parts) was added and thereactants were stirred under nitrogen for 20 hours at 180° C. Aftercooling to 20° C., the polyester was obtained as a waxy solid.

Intermediate F

Tolylene diisocyanate (48.02 parts) was added to a reaction vesselheated to 50° C. under nitrogen. Intermediate D (400 parts) was addedover 2 hrs with agitation at 50-60° C. The reaction was continued withstirring at 60° C. for 1 hour. The reactants were then cooled to 20° C.and diethanolamine (28.99 parts) was added. The reaction was continuedwith stirring at 35° C. until no isocyanate remained.Di-tert-butyl-4-methylphenol (0.24 parts) was then added.

Intermediate G

Hydroxyethyl acrylate (71.38 parts), ε-caprolactone (666.73 parts) andδ-valerolactone (215.44 parts), 4-methoxy phenol (0.95 parts), tin(II)chloride (0.047 parts) were stirred together under an air atmosphere at125° C. The reaction was allowed to continue at this temperature for 20hours. After cooling to 20° C., the polyester was obtained as a waxysolid.

Intermediate H

1-Dodecanol (64.1 parts) and ε-caprolactone (509.97 parts) were stirredtogether under nitrogen at 150° C. Zirconium butoxide catalyst (2.9parts) was added and the reactants were stirred under nitrogen for 20hours at 180° C. After cooling to 20° C., the polyester was obtained asa waxy solid. This is Polyester 3.

Tolylene diisocyanate (41.71 parts) was added to a reaction vesselheated to 50° C. under nitrogen. Polyester 3 (400 parts) was warmed to50° C. in an oven then added to the reaction vessel over 2 hrs withagitation at 50-60° C. The reaction was continued with stirring at 60°C. for 1 hour. The reactants were then cooled to 20° C. anddiethanolamine (25.18 parts) was added. The reaction was continued withstirring at 35° C. until no isocyanate remained.

In the following examples the molecular weight of the dispersantsproduced were characterized by size exclusion chromatography. The numberaverage molecular weight (Mn) and weight average molecular weight (Mw)values were determined relative to polystyrene standards. Forpolymerizations carried out in solvent the final solids content of thesolution was determined by gravimetric analysis.

Dispersant 1

Dimethylolpropionic acid (7.4 parts, and often referred to as2,2-bis(hydroxymethyl)propionic acid), 1,4-cyclohexane dimethanol (7.88parts), Intermediate B (150.0 parts), 2-hydroxyethyl acrylate (4.2parts), and ethyl acetate (195 parts) were added to a round bottomedflask and heated with agitation to 70° C. under a nitrogen atmosphere.Dibutyltindilaurate (0.1 parts) in ethyl acetate (10 parts) was added.Tolylene diisocyanate (34.62 parts) was added to the reaction vesseldropwise over a period of 30 minutes maintaining the temperature at70-75° C. Reaction was allowed to continue at this temperature for afurther 28 hours when only a trace of isocyanate was detectable byinfrared analysis. Ethanol (10 parts) were added and butylated hydroxyltoluene (BHT) (0.02 parts) added as a free radical inhibitor.

Solids content was adjusted to 50 wt. % by addition of ethyl acetate tocompensate for small solvent evaporation losses (Mn=12,300 andMw=24,900).

Comparative Dispersant α

This polyurethane is very similar to example 1 but does not contain anycarbon to carbon double bonds. Dimethylolpropionic acid (7.8 parts),14-cyclohexane dimethanol (10.27 parts), Intermediate B (144.0 parts)1-butanol (2.93 parts) and ethyl acetate (180 parts) were added to around bottomed flask and heated with agitation to 70° C. under anitrogen atmosphere. Dibutyltindilaurate (0.1 parts) in ethyl acetate(10 parts) was added. Tolylene diisocyanate (37.83 parts) was added tothe reaction vessel dropwise over a period of 45 minutes maintaining thetemperature at 70-75° C. Reaction was allowed to continue at thistemperature for a further 28 hours when only a trace of isocyanate wasdetectable by infrared analysis. (Mn=12,300 and Mw=22,400).

Pigment Dispersion Performance

Dispersion Formulation:

Dispersions were prepared by adding dispersant 1 (8.0 parts) tomethoxypropyl acetate (22 parts) in a 4 oz glass jar. Black pigment (20parts, Printex 35, ex Degussa) was added and the mixture was gentlystirred to wet out the pigment. Glass beads (3 mm diameter, 125 parts)were added to the jar. The jar was placed in a Scandex disperser model200-K and the contents milled by oscillatory shaking for 2 hours. Thisis Millbase 1.

A solution of tetraethylpentamine (TEPA) (5.88 parts) in ethylacetate/ethanol (3/1) (100 parts) was prepared. The TEPA solution (0.063parts) was added to a portion of Millbase 1 (5 parts) together withethyl acetate/ethanol (3/1) (0.44 parts). This is Millbase 1A. Ethylacetate/ethanol (3/1) (0.50 parts) was added to a portion of Millbase 1(5 parts). This is Millbase 1B. The Millbases 1A and 1B (0.5 parts) werelet down into a nitrocellulose resin, NC DLX 3/5, (1.5 parts, ex NobelEnterprises). Millbases and inks were prepared in the same way usingDispersant α to produce Millbase α1 and Inks α1A and α1B.

A portion of the resulting inks were drawn down on to black and whitecard using a number 3 K-bar. A simple visual assessment was made of thedraw downs based on hiding power, jetness and gloss with a scoringsystem of 1 to 5. A score of 5 indicating the best performance. Acontrol experiment with no dispersant gave a let down with quality equalto 1.

The remaining portion of the inks was stored for 2 weeks at 52° C. Thestored inks were drawn down on to black and white in the same away andassessed to see if there had been any change on storage.

TABLE 1 Storage Ink Initial at Reference Rating 52° C. 1A Ink containsTEPA Dispersant 4 4 contains C═C 1B No TEPA No C═C 4/5 2 α1A Inkcontains TEPA No C═C 4 2/3 α1B No TEPA No C═C 4/5 2.

Only for the ink 1A was there no reduction in quality of the drawdownafter 2 weeks storage of the ink at 52° C. For ink 1A both thedispersant used contained carbon to carbon double bonds and TEPA waspresent in the formulation.

Dispersant 2

Cyclohexane dimethanol (8.57 parts), Intermediate B (165.0 parts),2,2-bis(hydroxymethyl)propionic acid (8.14 parts), hydroxyethyl acrylate(4.6 parts) and ethyl acetate (224.6 parts) were stirred under nitrogenat 70° C. Dibutyltin dilaurate (0.15 parts) was then added. Tolylenediisocyanate (37.96 parts) charged to the reaction mixture over 60minutes. The reaction mixture was stirred under nitrogen for a further20 hours at 70° C. until no isocyanate remained. Solids content was 51wt. % (Mn=7,600 and Mw=19,900).

Dispersant 3

Cyclohexane dimethanol (9.98 parts), Intermediate B (144.0 parts),2,2-bis(hydroxymethyl)propionic acid (8.00 parts), poly(propyleneglycol) acrylate (18.71 parts) and ethyl acetate (218.71 parts) werestirred under nitrogen at 70° C. Dibutyltin dilaurate (0.1 parts) wasthen added. Tolylene diisocyanate (37.72 parts) charged to the reactionmixture over 72 minutes. The reaction mixture was stirred under nitrogenfor a further 20 hours at 70° C. until no isocyanate remained. Solidscontent was 50 wt. % (Mn=6,300 and Mw=23,800).

Dispersant 4

Cyclohexane dimethanol (10.18 parts), Intermediate B (144.0 parts),2,2-bis(hydroxymethyl)propionic acid (7.8 parts), caprolactone2-(methacryloyloxy)ethyl ester (13.56 parts) and ethyl acetate (213.56parts) were stirred under nitrogen at 70° C. Dibutyltin dilaurate (0.1parts) was then added. Tolylene diisocyanate (37.72 parts) charged tothe reaction mixture over 30 minutes. The reaction mixture was stirredunder nitrogen for a further 20 hours at 70° C. until no isocyanateremained. Solids content was 51 wt. % (Mn=6,300 and Mw=19,400).

Sheet Molding Examples.

To demonstrate that these materials will be reactive in a sheet moldingcompound type formulation the coreactivity with styrene wasinvestigated.

Copolymerization of dispersants 2, 3 and 4 with styrene.

Styrene (10 parts), dispersant (ca. 21 parts ca. 50 wt. % in ethylacetate) and toluene (10 g) were charged to a schlenk tube under anitrogen atmosphere followed by 2,2′-azobis(2-methylpropionitrile) (0.1parts). The contents were heated for 20 hours at 70° C. then cooled toroom temperature. In each case the product of the reaction was gelconsistent with a cross linking reaction having occurred between thedispersant and styrene.

To show that gellation did not occur in the absence of the dispersants ahomo-polymerization of styrene was carried out under similar conditions.Styrene (10 parts) and toluene (20 parts) were charged to a schlenk tubeunder a nitrogen atmosphere followed by2,2′-azobis(2-methylpropionitrile) (0.1 parts). The contents were heatedfor 20 hours at 70° C. then cooled to room temperature yielding asolution of polystyrene as a clear pourable liquid.

Dispersant 5

N-methyldiethanolamine (2.83 parts), Intermediate A (40.8 parts, 50%solution in methoxypropyl acetate), caprolactone2-(methacryloyloxy)ethyl ester (1.72 parts) and methoxypropyl acetate(11.3 parts) were stirred under nitrogen at 70° C. Dibutyltin dilaurate(0.03 parts) was then added. Tolylene diisocyanate (6.74 parts) wascharged to the reaction mixture over 21 minutes. The reaction mixturewas stirred under nitrogen for a further ca. 3 hours at 70° C. until noisocyanate remained. Solids content was 56 wt. % (Mn=8,300 andMw=25,800).

Dispersant 6

Intermediate B (32.64 parts), cyclohexane dimethanol (5.30 parts),poly(propylene glycol) methacrylate (3.66 parts), dibutyltin dilaurate(0.05 parts) and methoxypropyl acetate (51.66 parts) were added to around bottom flask and heated with agitation to 70° C. under a nitrogenatmosphere. Tolylene diisocyanate (10.0 parts) was added drop wise overa period of 30 minutes maintaining the temperature at 70-75° C. Thereaction was allowed to continue at this temperature for a further 4hours when only a trace of isocyanate remained. (Mn=11,400 andMw=34,600).

Dispersant 7

Intermediate B (74.00 parts), hexane diol (7.33 parts), hydroxylethylacrylate (2.25 parts), dibutyltin dilaurate (0.1 parts) andmethoxypropyl acetate (102.25 parts) were added to a round bottom flaskand heated with agitation to 70° C. under a nitrogen atmosphere.Tolylene diisocyanate (18.57 parts) was added drop wise over a period of30 minutes maintaining the temperature at 70-75° C. The reaction wasallowed to continue at this temperature for a further 4 hours when onlya trace of isocyanate remained. Di-tert-butyl-4-methylphenol (0.01parts) was then added. Solids content was 49 wt. % (Mn=11,800 andMw=41,100).

Dispersant 8

Intermediate A (32.64 parts), cyclohexane dimethanol (5.07 parts),caprolactone 2-(methacryloyloxyethyl)ester (2.61 parts), dibutyltindilaurate (0.05 parts) and methoxypropyl acetate (50.61 parts) wereadded to a round bottom flask and heated with agitation to 70° C. undera nitrogen atmosphere. Tolylene diisocyanate (10.24 parts) was addeddrop wise over a period of 30 minutes maintaining the temperature at70-75° C. The reaction was allowed to continue at this temperature for afurther 4 hours when only a trace of isocyanate remained. Solids contentwas 50 wt. % (Mn=7,800 and Mw=26,700).

Dispersant 9

Intermediate A (19.72 parts), N-methyldiethanolamine (2.85 parts),hydroxyethyl methacrylate (0.46 parts), dibutyltin dilaurate (0.03parts) and methoxypropyl acetate (29.46 parts) were added to a roundbottom flask and heated with agitation to 70° C. under a nitrogenatmosphere. Tolylene diisocyanate (6.40 parts) was added drop wise overa period of 30 minutes maintaining the temperature at 70-75° C. Thereaction was allowed to continue at this temperature for a further 4hours when only a trace of isocyanate remained. Solids content was 50wt. % (Mn=5,300 and Mw=12,200).

Dispersant 10

Tolylene diisocyanate (49.75 parts) was added to a round bottom flaskunder a nitrogen atmosphere. With agitation, intermediate B (192.40parts), hexane diol (9.29 parts), N-methyldiethanolamine (8.16 parts),hydroxyethyl methacrylate (12.39 parts) and di-tert-butyl-4-methylphenol(0.15 parts) were added over a period of 30 minutes and the contentsexothermed to 50-55° C. The reaction was heated to 70-75° C. for afurther 1.5 hours. Dibutyltin dilaurate (0.3 parts) was then added andthe contents maintained at 70-75° C. for 20 hours. Hydroxyethylmethacrylate (1.2 parts) was then added and the polymerisationmaintained at 70-75° C. for 30 minutes when only a trace of isocyanateremained. (Mn=6,400 and Mw=18,000).

Dispersant 11

Tolylene diisocyanate (19.42 parts) was added to a round bottom flaskunder a nitrogen atmosphere. With agitation, intermediate C (74 parts),N-methyldiethanolamine (6.58 parts), hydroxyethyl acrylate (4.32 parts)and di-tert-butyl-4-methylphenol (0.05 parts) were added over a periodof 30 minutes and the contents exothermed to 50-55° C. The reaction washeated to 70-75° C. for a further 4 hours until only a trace ofisocyanate remained. (Mn=4,200 and Mw=15,700).

Dispersant 12

Intermediate B (228.00 parts) and 2,2-bis(hydroxymethyl)propionic acid(19.23 parts) were added to a round bottom flask with agitation under anitrogen atmosphere. Tolylene diisocyanate (52.47 parts) was then addedand the temperature exothermed to 40-45° C. Hydroxyethyl methacrylate(13.07 parts), dibutyltin dilaurate (0.3 parts) anddi-tert-butyl-4-methylphenol (0.16 parts) were then added and thecontents heated to 70-75° C. The reaction was maintained at 70-75° C.for 20 hrs until no isocyanate remained. (Mn=8,400 and Mw=17,300).

Dispersant 13

Intermediate B (60.0 parts), 2,2-bis(hydroxymethyl)propionic acid (3.0parts), hexane diol (10.37 parts), Intermediate D (40.16 parts),dibutyltin dilaurate (0.1 parts), di-tert-butyl-4-methylphenol (0.14parts) and methoxypropyl acetate (140.16 parts) were added to a roundbottom flask and heated with agitation to 70° C. under a nitrogenatmosphere. Tolylene diisocyanate (26.53 parts) was added drop wise overa period of 30 minutes maintaining the temperature at 70-75° C. Thereaction was allowed to continue at this temperature for a further 20hours when only a trace of isocyanate remained. (Mn=6,900 andMw=24,500).

Dispersant 14

Intermediate F (71.0 parts), N-methyldiethanolamine (3.0 parts), hexanediol (5.41 parts), Intermediate E (18.14 parts), dibutyltin dilaurate(0.1 parts), di-tert-butyl-4-methylphenol (0.1 parts) and ethyl acetate(118.14 parts) were added to a round bottom flask and heated withagitation to 70° C. under a nitrogen atmosphere. Tolylene diisocyanate(20.49 parts) was added drop wise over a period of 30 minutesmaintaining the temperature at 70-75° C. The reaction was allowed tocontinue at this temperature for a further 3 hours when only a trace ofisocyanate remained. Solids content was 55 wt. % (Mn=6,700 andMw=22,000).

Dispersant 15

Intermediate F (60.0 parts), hexane diol (11.79 parts), Intermediate D(78.0 parts), dibutyltin dilaurate (0.1 parts),di-tert-butyl-4-methylphenol (0.18 parts) and butyl acetate (178.0parts) were added to a round bottom flask and heated with agitation to70° C. under a nitrogen atmosphere. Tolylene diisocyanate (28.11 parts)was added drop wise over a period of 30 minutes maintaining thetemperature at 70-75° C. The reaction was allowed to continue at thistemperature for a further 3 hours when only a trace of isocyanateremained. Solids content was 50 wt. % (Mn=5,200 and Mw=9,200).

Dispersant 16

Intermediate C (60.0 parts), N-methyldiethanolamine (8.0 parts), hexanediol (4.15 parts), Intermediate G (76.31 parts),di-tert-butyl-4-methylphenol (0.1 parts) were added to a round bottomflask and heated with agitation to 70° C. under a nitrogen atmosphere.Tolylene diisocyanate (27.75 parts) was added drop wise over a period of30 minutes maintaining the temperature at 70-75° C. The reaction wasallowed to continue at this temperature for a further 2 hours when onlya trace of isocyanate remained. (Mn=7,300 and Mw=19,800).

Dispersant 17

Intermediate H (126.14 parts), 2,2-bis(hydroxymethyl)propionic acid (4.1parts), hexane diol (4.0 parts), hydroxyethyl methacrylate (7.86 parts),di-tert-butyl-4-methylphenol (0.05 parts), dibutyltin dilaurate (0.1parts) and ethyl acetate (50.8) were added to a round bottom flask andheated with agitation to 70° C. under a nitrogen atmosphere. Tolylenediisocyanate (22.80 parts) was added drop wise over a period of 30minutes maintaining the temperature at 70-75° C. The reaction wasallowed to continue at this temperature for a further 20 hours when onlya trace of isocyanate remained. The majority of solvent was then removedon a rotary evaporator. The material was transferred to a metal tray andthe product further dried in a vacuum oven. (Mn=1600 and Mw=10,600).

Dispersant 18

Tolylene diisocyanate (52.19 parts) was added to a round bottom flaskunder a nitrogen atmosphere. With agitation, intermediate B (210 parts),1,1′-{[3-(dimethylamino)-propyl]imino}bis-2-propanol (37.81 parts),hydroxyethyl acrylate (6.33 parts) and di-tert-butyl-4-methylphenol(0.31 parts) were added over a period of 30 minutes and the contentsexothermed to 50-55° C. The reaction was heated to 70-75° C. for afurther 4 hours until only a trace of isocyanate remained. Solidscontent was 52.0 wt. % (Mn=6,700 and Mw=20,900).

Dispersant 19

Dispersant 18 (300 parts) was added to a round bottom flask and heatedto 70° C. under nitrogen with agitation. Benzyl chloride (9.4 parts) andmethoxypropyl acetate (9.4 parts) was then added and the reactionmaintained at 70° C. for 20 hours. The product was a viscous liquid.Solids content was 53.0 wt. %.

Dispersant 20

Tolylene diisocyanate (26.48 parts) was added to a round bottom flaskunder a nitrogen atmosphere. With agitation, intermediate C (105 parts),1,1′-{[3-(dimethylamino)-propyl]imino}bis-2-propanol (18.52 parts) andhydroxyethyl methacrylate (3.6 parts) were added over a period of 30minutes and the contents exothermed to 50-55° C. The reaction was heatedto 70-75° C. for a further 4 hours until only a trace of isocyanateremained. (Mn=5,500 and Mw=22,400).

Dispersant 21

Hexanediol (13.9 parts), Intermediate B (207.0 parts),2,2-bis(hydroxymethyl)propionic acid (15.45 parts), hydroxyethylmethacrylate (8.61 parts), butylated hydroxytoluene (0.001 parts) andmethoxypropyl acetate (308.6 parts) were stirred under air at ca. 23° C.Dibutyltin dilaurate (0.30 parts) was then added. Tolylene diisocyanate(63.35 parts) charged to the reaction mixture over ca. 5 mins. resultingin a small exotherm. The reaction mixture was then heated to 70-72° C.and stirred under air for a further 20.5 hours until only a slight traceof isocyanate remained by infra red analysis. Solids content was 50.8wt. % (Mn=6,900 and Mw=21,400).

Dispersant 22

Hexanediol (13.08 parts), Intermediate A (414.0 parts, 50 wt % solutionin methoxypropyl acetate), 2,2-bis(hydroxymethyl)propionic acid (15.45parts), hydroxyethyl acrylate (7.78 parts), Butylated hydroxytoluene(0.001 parts) and methoxypropyl acetate (100.8 parts) were stirred underair at ca. 24° C. Dibutyltin dilaurate (0.30 parts) was then added.Tolylene diisocyanate (64.17 parts) was charged to the reaction mixtureover ca. 18 mins. resulting in an exotherm to 56° C. The reactionmixture was then heated to 70-73° C. and stirred under air for a furtherca. 19.3 hours until no isocyanate remained by infra red analysis.Solids content was 49.6 wt. % (Mn=4,200 and Mw=13,200).

Dispersant 23

Hexanediol (12.03 parts), Intermediate A (414.0 parts 50 wt. % solutionin methoxypropyl acetate), NMDA (15.45 parts), hydroxyethyl methacrylate(8.86 parts), butylated hydroxytoluene (0.001 parts) and methoxypropylacetate (101.9 parts) were stirred under air at ca. 22° C. Dibutyltindilaurate (0.30 parts) was then added. Tolylene diisocyanate (65.22parts) was charged to the reaction mixture over ca. 8 mins. resulting inan exotherm to 54° C. The reaction mixture was then heated to 70-73° C.and stirred under air for a further ca. 3 hours until no isocyanateremained by infra red analysis. Solids content was 48.8 wt. % (Mn=7,200and Mw=22,500).

Dispersant 24

Cyclohexane dimethanol (1.76 parts), Intermediate B (93.78 parts),2,2-bis(hydroxymethyl)propionic acid (5.35 parts), hydroxyethyl acrylate(2.49 parts), trimethylolpropane (0.97 parts) and ethyl acetate (125parts) were stirred under nitrogen at 70° C. Dibutyltin dilaurate (0.098parts) was then added. Tolylene diisocyanate (20.55 parts) charged tothe reaction mixture over 30 minutes. The reaction mixture was stirredunder nitrogen for a further 25.5 hours at 70° C. until no isocyanateremained. Solids content was 53.0 wt. % (Mn=12,500 and Mw=31,000).

Dispersant 25

Cyclohexane dimethanol (2.73 parts), Intermediate B (145.51 parts),2,2-bis(hydroxymethyl)propionic acid (8.3 parts), hydroxyethyl acrylate(2.70 parts), pentaerythritol triacrylate (9.93 parts),trimethylolpropane (1.50 parts) and ethyl acetate (185 parts) werestirred under nitrogen at 70° C. Dibutyltin dilaurate (0.15 parts) wasthen added. Tolylene diisocyanate (20.55 parts) charged to the reactionmixture over 30 minutes. The reaction mixture was stirred under nitrogenfor a further 25.5 hours at 70° C. until no isocyanate remained. Solidscontent was 53.0 wt. % (Mn=15,700 and Mw=42,600).

Pigment Dispersion Performance Dispersion of Carbon Black in Styrene

Dispersion Formulation CB1

A dispersion was prepared by dissolving dispersant (1.0 parts) anddi-tert-butyl-4-methylphenol (0.05 parts) in styrene (5.5 parts). 3 mmglass beads (17 parts) and black pigment (3.5 parts, Raven 1200, exColumbian Chemicals Company) were added and the contents milled on ahorizontal shaker for 16 hrs.

Dispersion Formulation CB2a

A dispersion was prepared by dissolving dispersant (1.0 parts ca. 50 wt% in solvent) in styrene (5.5 parts). 3 mm glass beads (17 parts) andblack pigment (3.5 parts, Raven 1200, ex Columbian Chemicals Company)were added and the contents milled on a horizontal shaker for 16 hrs.

Dispersion Formulation CB2b

A dispersion was prepared by dissolving dispersant (2.0 parts ca. 50 wt.% in solvent) in styrene (4.5 parts). 3 mm glass beads (17 parts) andblack pigment (3.5 parts, Raven 1200, ex Columbian Chemicals Company)were added and the contents milled on a horizontal shaker for 16 hrs.

Dispersion Formulation CB3

A dispersion was prepared by dissolving dispersant (1.4 parts 100%active) in styrene (19.6 parts). 3 mm glass beads (125 parts) and blackpigment (14.0 parts, Raven 1200, ex Columbian Chemicals Company) wereadded and the contents milled on a Red Devil shaker for 1 hr.

Dispersion Formulation CB4a

A dispersion was prepared by dissolving dispersant (3.26 parts 100%active) in styrene (18.14 parts). 3 mm glass beads (125 parts) and blackpigment (13.6 parts, Raven 1200, ex Columbian Chemicals Company) wereadded and the contents milled on a Red Devil shaker for 1 hr.

Dispersion Formulation CB4b

A dispersion was prepared by dissolving dispersant (6.52 parts ca. 50wt. % in solvent) in styrene (15.15 parts). 3 mm glass beads (125 parts)and black pigment (13.6 parts, Raven 1200, ex Columbian ChemicalsCompany) were added and the contents milled on a Red Devil shaker for 1hr.

Summary of Dispersion Performance

In the absence of a dispersant in the formulations, formed a thickinhomogeneous immovable gel with regions in which the pigment was notwetted.

In the presence of dispersants, the pigment milled to form a paste. Theviscosity of the paste has been determined in the table below bydetermining the freedom of the glass beads to move throughout the millbase. In all cases the pigment was wetted out and a homogeneousdispersion formed.

Viscosity Grading

A=Very Fluid

B=Fluid

C=Viscous

TABLE 2 to Show Performance of Dispersants 6-20 Carbon Black DispersionViscosity of Dispersion Dispersant Formulation Used Dispersion D6  6CB2a B D7  7 CB2b B D8  8 CB2a A D9  9 CB1 B D10 10 CB3 C D11 11 CB4a AD12 12 CB3 C D13 13 CB4b A D14 14 CB4b A D15 15 CB4b C D16 16 CB4a B D1717 CB4a A D18 18 CB4b C D19 19 CB4b C D20 20 CB4a C D21 21 CB2b A D22 22CB2b A D23 23 CB2b A

For dispersion D17, the viscosity of the dispersion was measured on a TAInstruments AR2000 Rheometer. Approximately 1 ml of the dispersion wasapplied to the peltier plate and the measuring geometry (a 40 nm 2°steel cone) was then lowered onto the sample. A shear rate sweep of 0.04to 2000 was then applied to the sample whilst maintaining a constanttemperature of 25° C. The viscosity of the dispersion was as shown inthe following table.

TABLE 3 Viscosity/Pa · s Viscosity/Pa · s Dispersion (shear rate 1 s⁻¹)(shear rate 1000 s⁻¹) D17 0.6 0.1Testing in a UV Cure Formulation.

The presence of reactive double bonds in the dispersant has been shownto have a beneficial effect in a model UV curing system.

Comparison was made between a formulation containing dispersant 1 ofthis invention and comparative dispersant α with a similar compositionexcept that it does not contain reactive double bonds. Formulations UV1and UVα were prepared from the following materials.

TABLE 4 UV1 UVα Parts by weight Parts by weight Tripropylene Glycol 9.009.00 Diacrylate Dispersant 1 1.00 — Comparative Dispersant α — 1.00Tegorad 2250¹ 0.40 0.40 Irgacure 819² 3.30 3.30 Darocure 1173² 6.70 6.70¹Supplied by Tego Chemie ²Supplied by Ciba Specialty Chemicals

Films were of UV1 and UVα were drawn down onto glass panels using a Kbar number 0. The coated panels were cured in a Fusion Systems UVapparatus by being passed under 10″ long D bulb (with a power rating of120 watts/cm) at a speed of ca. 40 m/min.

After 7 passes under the lamp the film from formulation UV1 had a Koenighardness of 31 seconds. The comparative coating from formulation UVαonly had a Koenig hardness of 24 seconds.

Another film coated similarly from formulation UV1 achieved a Koenighardness of 26 seconds after five passes under the UV lamp.

These observations demonstrate that coating from UV1 produced of aharder film after an equivalent cure time or a required a shorter curetime to achieve the same hardness relative to the formulation containingthe comparative dispersant α without reactive double bonds.

Blue UV Ink Formulations

Dispersions were prepared by adding the materials detailed in thefollowing table to a 4 oz. glass jar in the order listed.

TABLE 5 UV Ink Color Dispersion Formulation (blue) With No DispersantDisper- Disper- Disper- Disper- Comparative sant 1 sant 21 sant 22 sant23 Heliogen Blue 7.00 7.00 7.00 7.00 7.00 D7080¹ Dispersant 1 8.40Dispersant 21 8.27 Dispersant 22 8.47 Dispersant 23 8.61 Solsperse 5000²0.77 0.77 0.77 0.77 Tripropyleneglycol 40.00 30.80 30.93 30.73 30.59diacrylate TOTAL 46.97 46.97 46.97 46.97 46.97 ¹Supplied by BASF²Supplied by Lubrizol Advanced Materials, Inc.

The mixture was gently stirred to wet out the pigment. 125 parts of 3 mmdiameter glass beads were added to the jar. The jar was placed in aScandex disperser model 200-K and the contents milled by oscillatoryshaking for 4 hours.

Blue UV inks were then prepared by adding 3.21 parts of each of thedispersions to a mixture of the following components.

TABLE 6 UV Ink Formulations from the above Dispersions Parts by weightEbecryl 160¹ 3.50 Ebecryl 83¹ 2.75 Tegorad 2250² 0.10 Irgacure 819³ 0.83Darocure 1173³ 1.68 Tripropyleneglycol Diacrylate 3.25 IsobornylAcrylate 10.10 ¹Supplied by UCB Chemicals ²Tego Chemie ³Supplied by CibaSpecialty Chemicals

The resulting inks were drawn down onto Leneta black and white cardusing an automatic film applicator fitted with a number 0 K bar. Thecoatings were cured in a Fusion Systems UV apparatus by being passed 4times under 10″ long D bulb (with a power rating of 120 watts/cm) at aspeed of ca. 40 m/min.

The gloss and haze of the coatings were measured with a gloss and hazemeter. The ink containing dispersants produced a glossier coating withmuch higher color strength than the comparative ink without a dispersantpresent.

TABLE 7 Data on Gloss, Haze and Strength of Blue UV Ink FormulationsStrength Gloss 20° Haze (%) Blue ink no dispersant from UV blue 66.578.5 100 comparative Blue ink from dispersion UV blue 1 72.2 45.9 197.7Blue ink from dispersion UV blue 21 73.3 49.4 196.7 Blue ink fromdispersion UV blue 22 75.7 47.3 201.6 Blue ink from dispersion UV blue23 73.8 44.7 203.2Yellow UV Ink Formulations

Dispersions were prepared by adding the materials detailed in thefollowing table 8 to a 4 oz. glass jar in the order listed.

TABLE 8 UV Yellow Ink Dispersions, Comparative and Dispersants 1, 21,22, and 23 Disper- Disper- Disper- Disper- Comparative sant 1 sant 21sant 22 sant 23 Ink Jet Yellow 4G 6.80 6.80 6.80 6.80 6.80 VP 2532¹Dispersant 1 5.44 Dispersant 21 5.35 Dispersant 22 5.48 Dispersant 235.57 Tripropyleneglycol 38.16 32.28 32.37 32.24 32.15 diacrylate TOTAL44.96 44.96 44.96 44.96 44.96 ¹Supplied by Clariant

The mixture was gently stirred to wet out the pigment. 125 parts of 3 mmdiameter glass beads were added to the jar. The jar was placed in aScandex disperser model 200-K and the contents milled by oscillatoryshaking for 4 hours.

Yellow UV inks were then prepared by adding 3.21 parts of each of thedispersions to a mixture of the following components.

TABLE 9 Yellow UV Ink Formulations Parts by weight Ebecryl 160¹ 3.50Ebecryl 83¹ 2.75 Tegorad 2250² 0.10 Irgacure 819³ 0.83 Darocure 1173³1.68 Tripropyleneglycol Diacrylate 3.25 Isobornyl Acrylate 10.10¹Supplied by UCB Chemicals ²Tego Chemie ³Supplied by Ciba SpecialtyChemicals

The resulting inks were drawn down onto Leneta black and white cardusing an automatic film applicator fitted with a number 0 K bar. Thecoatings were cured in a Fusion Systems UV apparatus by being passed 4times under 10″ long D bulb (with a power rating of 120 watts/cm) at aspeed of ca. 40 in/min.

The gloss and haze of the coatings were measured with a gloss and hazemeter. The ink containing dispersants produced a glossier coating withhigher color strength than the comparative ink without a dispersantpresent.

TABLE 10 Data on Gloss, Haze and Strength of Yellow UV Ink FormulationsGloss Strength 20° Haze (%) Yellow ink no dispersant from dispersion68.3 79.4 100 UV yellow comparative Yellow ink from dispersion UV yellow1 76.2 51.3 110.3 Yellow ink from dispersion UV yellow 21 75.6 56.0115.0 Yellow ink from dispersion UV yellow 22 81.0 56.6 126.2 Yellow inkfrom dispersion UV yellow 23 87.1 60.9 131.8UV Cured Ink and Coating Formulations

TABLE 11 Mill base Formulations with Solsperse ® X300 and SelectedExample Dispersants 1-25 for Ink Jet printing application ComponentMillbase 1 Millbase 2 Millbase 3 Millbase 4 Monomer SR 492 40-60% 40-60%40-60% 40-60% Sartomer, Warrington, PA Monomer CN 15-25% 15-25% 15-25%15-25% ” 2262/2282 Pigment PB15.3 - Hostaperm 15-30% Clariant, Blue PBFCoventry, RI PV19 - Hostaperm Red 15-30% Clariant, EFB02 Coventry, RIPY139 - Novaperm 15-30% Clariant, Yellow PM3R Coventry, RI CarbonBlack - Special 15-30% Degussa, Black 250 Frankfurt, Germany Solsperse ®X300 or  5-120%  5-120%  5-120%  5-120% Experimental selections fromDispersants 1-25 Solsperse 5000 as 0-1% 0-1% 0-1% 0-1% Lubrizol,synergist Total 100% 100% 100% 100% *Millbase viscosity target is around200-1500 cpsLet-Down Formulation for Millbases 1-4 into a Pigmented Ink/Coating

Oligomer Photoinitiators Formula CD420 SR492/CN2262 Irgacure 369 EsacureKS300 Esacure TZT Esacure ITX Defoamer BYK Total Millbase 1-4 (Sartomer)(Sartomer) (Ciba) (Sartomer) (Sartomer) (Sartomer) 088 Weight (g) 15-40% 60-80% 0-10% 1-2% 2-4% <1% <1% 0.5% 100.00 2 5-40% 60-80% 0-10%1-2% 2-4% 0.50 0.25 0.25 100.00 *Ciba, Basel, Switzerland; BYK-Chemie,Wallingford, CTThe letdowns were then rolled onto Leneta opacity charts and attemptedto be cured with a UVA lamp at 50 fpm and 300 WPI.Viscosity target for the final ink should be from 5-15 cps at operatingtemperature of 25 to 70 C with a surface tension of 30-35 dynes/cmPhysical Properties to be TestedCure TimeBlock resistanceMEK Rub resistanceWater sensitivityCoatings with Nano-Particle Formulation:

TABLE 12 Solsperse ® Oligomer Photoinitiators X300 or CD420 SR492/CN2262Irgacure Esacure KS300 Esacure TZT Esacure ITX Defoamer BYK selectionsfrom Nano-alumina (Sartomer) (Sartomer) 369 (Ciba) (Sartomer) (Sartomer)(Sartomer) 088 Dispersants 1-25 dispersion Control 60-80% 0-10% 1-2%2-4% <1% <1% 0.5% 0-5 0 Nano 60-80% 0-10% 1-2% 2-4% 0.50 0.25 0.25 1-51-20* wt. % *the dispersion has nano-alumina particles from 5-50%The following test will be conducted and compared with Control (withoutnano-particles) with a nano-alumina particle containing coating todetermine if the nano-aluminum particles with varying levels ofdispersants provide extra hardness and abrasion resistance to thecoating. The nano-particles are sourced from Alfa Aesar and are made byNano-phase Technologies in Romeoville, Ill.Tabor Scratch test—“A” Prong, 4 lbs, 50 cyclesPencil Hardness—Red Asia PencilsScuff Test—3 lb, 3 passes using A prong from Tabor TestScrub Test—200 cycles with scrub pad, gloss measure in same area beforeand after

INDUSTRIAL APPLICATION

Dispersions and mill bases made from the composition of the inventionare particularly suitable for use in paints, including high solidspaints, solvent based inks, especially ink jet, flexographic, gravure,and screen inks, UV cure inks, thermal/IR curable inks, color filterlayers for display screen equipment, thermosetting resin compositionssuch as sheet molding compounds, bulk molding compounds or gel coats andnon-aqueous ceramic processes, coatings with or without nano-materialssuch as metal oxides, metal, nanotubes, etc.

The dispersants may also be used for dispersing particulate matterincluding pigments in powder coating formulations particularly powdercoatings which are to be cured by radiation curing.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention maybe used together with ranges or amounts for any of the other elements.As used herein, the expression “consisting essentially of” permits theinclusion of substances that do not materially affect the basic andnovel characteristics of the composition under consideration.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thedisclosure. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

The invention claimed is:
 1. A millbase, paint, coating, or ink whichcomprises a particulate solid, a film-forming resin or polymerizableprecursor to a film-forming resin, a vehicle in which said particulatesolid is dispersed, and a polyurethane dispersant, wherein saidpolyurethane dispersant comprises a polyurethane backbone and attachedsolvent-solubilizing polyether chains of poly(C₂₋₄-alkylene oxide) ormixtures of polyether chains of poly(C₂₋₄-alkylene oxide) and polyesterchains, and optionally one or more chain terminators; further comprisinga nitrogen in a non-reactive amine (non-reactive with respect toisocyanates) laterally attached to the polyurethane backbone such thatsaid nitrogen atom is separated by at least two atoms from the closestatom on the backbone and wherein the non-reactive amine is derived fromthe chemical group consisting of N,N-bis(2-hydroxyethyl)isonicotinamide;1,1′-{[3-(dimethylamino)-propyl]imino}bis-2-propanol; or the compound

formed from the Michael addition of dimethylaminopropylamine and2-hydroxyethyl acrylate and wherein said non-reactive amine is atertiary amine, a quaternary ammonium salt, or combinations thereof andwherein on average each polyurethane dispersant molecule has at leastone reactive carbon to carbon double bond in either the backbone, thesolvent solubilizing chains, the chain terminators, or combinationsthereof.
 2. The millbase, paint, coating, or ink according to claim 1,wherein said polyurethane dispersant has been adsorbed onto saidparticulate solid and partially or fully chain extended or crosslinkedthrough chemical reactions of said reactive carbon to carbon double bondof said dispersant.
 3. A millbase, paint, coating, or ink according toclaim 1, utilized as an ink.
 4. A millbase, coating composition, ink, ormolding compound comprising a dispersed particulate solid, a freeradically polymerizable monomer, and a polyurethane dispersant, whereinsaid polyurethane dispersant comprises a polyurethane backbone andattached solvent-solubilizing polyether chains of poly(C₂₋₄-alkyleneoxide) or mixtures of polyether chains of poly(C₂₋₄-alkylene oxide) andpolyester chains, and optionally one or more chain terminators; furthercomprising a nitrogen in a non-reactive amine (non-reactive with respectto isocyanates) laterally attached to the polyurethane backbone suchthat said nitrogen atom is separated by at least two atoms from theclosest atom on the backbone and wherein the non-reactive amine isderived from the chemical group consisting ofN,N-bis(2-hydroxyethyl)isonicotinamide;1,1′-{[3-(dimethylamino)-propyl]imino}bis-2-propanol; or the compound

formed from the Michael addition of dimethylaminopropylamine and2-hydroxyethyl acrylate and wherein said non-reactive amine is atertiary amine, a quaternary ammonium salt, or combinations thereof andwherein on average each polyurethane dispersant molecule has at leastone reactive carbon to carbon double bond in either the backbone, thesolvent solubilizing chains, the chain terminators, or combinationsthereof.
 5. The millbase, coating composition, ink, or molding compoundof claim 4, wherein said reactive carbon to carbon double bond of saiddispersant is characterized such that it co-polymerizes with said freeradically polymerizable monomer.
 6. The millbase, coating composition,ink, or molding compound of claim 5, wherein said millbase, coatingcomposition, or ink are UV and/or thermally curable.
 7. A compositioncomprising a particulate solid, a vehicle in which the particulate solidis dispersed and a polyurethane dispersant, wherein said polyurethanedispersant comprises a polyurethane backbone and attachedsolvent-solubilizing polyether chains of poly(C₂₋₄-alkylene oxide) ormixtures of polyether chains of poly(C₂₋₄-alkylene oxide) and polyesterchains, and optionally one or more chain terminators; further comprisinga nitrogen in a non-reactive amine (non-reactive with respect toisocyanates) laterally attached to the polyurethane backbone such thatsaid nitrogen atom is separated by at least two atoms from the closestatom on the backbone and wherein the non-reactive amine is derived fromthe chemical group consisting of N,N-bis(2-hydroxyethyl)isonicotinamide;1,1′-{[3-(dimethylamino)-propyl]imino}bis-2-propanol; or the compound

formed from the Michael addition of dimethylaminopropylamine and2-hydroxyethyl acrylate and wherein said non-reactive amine is atertiary amine, a quaternary ammonium salt, or combinations thereof andwherein on average each polyurethane dispersant molecule has at leastone reactive carbon to carbon double bond in either the backbone, thesolvent solubilizing chains, the chain terminators, or combinationsthereof.
 8. The composition according to claim 7, wherein saidpolyurethane dispersant is at least partially adsorbed on the surface ofsaid particulate solid.
 9. The composition of claim 8, wherein saiddispersant is crosslinked or chain extended in a reaction usingadditional free radically co-polymerizable monomers.